膜科学与技术

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Preparation of crystalline/glassy MOF composite electrolytes
and performance in solid-state batteries

Authors： ZHU Junpeng, LI Jijia, JIANG Guangshen, AN Baigang

Units： School of Chemical Engineering, University of Science and Technology, Anshan 114051, China

KeyWords： solid-state electrolyte; metal-organic framework; MOF glass; grain boundary defects; hybrid electrolyte

ClassificationCode：TM911.3

year,volume(issue):pagination： 2026,46(2):119-130

Abstract：

Metal-organic framework (MOF) has garnered significant interest due to their high structural tunability and diverse ligand compositions. However, their application in solid-state electrolytes remains limited by two primary challenges: additional resistance arising from grain boundaries, and diminished Li+ mobility caused by the high migration rate of anions. In this study, a hybrid MOF-glass electrolyte membrane fabricated by incorporating crystalline MOF as fillers into a glassy MOF matrix was proposed. This design synergistically combined the advantages of the glassy and crystalline phases: the glassy phase eliminated grain-boundary resistance, facilitating rapid ion transport, while its long-range disordered structure promoted homogeneous ion migration, thereby suppressing dendrite growth. Meanwhile, the crystalline fillers preserved the intrinsic mass-transport pathways of the MOF. With an optimized mass ratio of ZIF-62 to ZIF-8 (9∶1), the as-prepared ZIF-62-based electrolyte (denoted as GZ-90) achieved a high Li+ conductivity of 4.727×10-4 S/cm along with favorable electrode interfacial compatibility. When applied in a quasi-solid-state LiFePO4 battery, the electrolyte enabled an initial capacity of 140.57 mA·h/g at 1 C and 25 ℃, with a capacity retention of 82.74% after 980 cycles.

Funds：

国家自然科学基金（52371224）；辽宁省科学技术计划项目（2025-MS-132）；辽宁科技大学高层次人才计划项目(6003000341)

AuthorIntro：

朱俊澎(2000-)，男，辽宁鞍山人，硕士研究生, 研究方向为MOF玻璃固态电解质

Reference：

[1]Lee Y G, Fujiki S, Jung C, et al. High-energy long-cycling all-solid-state lithium metal batteries enabled by silver-carbon composite anodes[J].Nat Energy, 2020, 5(4): 299-308.
[2]Duan S, Qian L, Zheng Y, et al. Mechanisms of the accelerated Li+ conduction in MOF-based solid-state polymer electrolytes for all-solid-state lithium metal batteries[J]. Adv Mater, 2024, 36(32): 2314120.
[3]He W, Li D, Guo S, et al. Redistribution of electronic density in channels of metal-organic frameworks for high-performance quasi-solid lithium metal batteries[J]. Energy Storage Mater, 2022, 47: 271-278.
[4]Yan Y, Liu Z, Li W, et al. Bioinspired design of vascularized glassy metal-organic frameworks electrolyte for quasi-solid-state sodium batteries[J]. Energy Storage Mater, 2025, 74: 103892.
[5]Wang T, Yuan H, Wang H, et al. Unlocking fast ionic transport in sub-nano channels of MOF-based electrolytes for next-generation batteries[J]. Adv Funct Mater, 2024, 34(45): 2405699.
[6]Li Y, Chen W, Lei T, et al. Reconstruction suppressed solid-electrolyte interphase by functionalized metal-organic framework[J]. Energy Storage Mater, 2023, 59: 102765.
[7]Xu R, Xu S, Wang F, et al. Double crosslinked polymer electrolyte by C-S-C Group and metal-organic framework for solid-state lithium batteries[J]. Small Struct, 2023, 4(3): 2200206.
[8]Dong P, Zhang X, Hiscox W, et al. Toward high-performance metal-organic-framework-based quasi-solid-state electrolytes: Tunable structures and electro-chemical properties[J]. Adv Mater, 2023, 35(32): 2211841.
[9]Huang W, Wang S, Zhang X, et al. Universal F4-modified strategy on metal-organic framework to chemical stabilize PVDF-HFP as quasi-solid-state electrolyte[J]. Adv Mater, 2023, 35(52): 2310147.
[10]Xiao C, Liu X, Li W, et al. Enhancing high voltage stability via fluorination of functionalized metal organic framework electrolyte in lithium metal batteries[J]. Batter Supercaps, 2024, 7(7): e202400078.
[11]Xu L, Xiao X, Tu H, et al. Engineering functionalized 2D metal-organic frameworks nanosheets with fast Li+ conduction for advanced solid li batteries[J]. Adv Mater, 2023, 35(38): 2303193.
[12]Li L, Jiang G, Wang K, et al. Engineering electronic inductive effect of linker in metal-organic framework glass toward fast-charging and stable-cycling quasi-solid-state lithium metal batteries[J]. Adv Funct Mater, 2025: 2505700.
[13]Kong O, Jiang G, Wang K, et al. Elucidation of Li+ conduction behavior in MOF glass electrolyte toward long-cycling and high C-rate lithium metal batteries[J]. Adv Energy Mater, 2025, 15(22): 2405593.
[14]宋昊, 张雅婷, 金花, 等. MOF玻璃膜研究进展[J]. 膜科学与技术, 2024, 44(6):132-144,157.
[15]叶茂, 奥德, 孙玉绣, 等. 新型自支撑ZIF玻璃膜的制备及气体分离性能[J]. 硅酸盐学报, 2024, 52(8):2545-2552.
[16]乔昂, 郭超慧, 王雷冲. 一种透明块体MOF玻璃的制备方法:中国, 202411164329.1[P]. 2025-01-07.
[17]Lin R, Chai M, Zhou Y, et al. Metal-organic framework glass composites[J]. Chem Soc Rev, 2023, 52(13): 4149-4172.
[18]Frentzel-Beyme L, Klo M, Kolodzeiski P, et al. Meltable mixed-linker zeolitic imidazolate frameworks and their microporous glasses: from melting point engineering to selective hydrocarbon sorption[J]. J Am Chem Soc, 2019, 141(31): 12362-12371.
[19]Bennett T D, Tan J C, Yue Y, et al. Hybrid glasses from strong and fragile metal-organic framework liquids[J]. Nat Commun, 2015, 6(1): 8079.
[20]Sun M, Li J, Yuan H, et al. Fast Li+ transport pathways of quasi-solid-state electrolyte constructed by 3D MOF composite nanofibrous network for dendrite-free lithium metal battery[J]. Mater Today Energy, 2022, 29: 101117.
[21]Chai S, Chang Z, Zhong Y, et al. Regulation of interphase layer by flexible quasi-solid block polymer electrolyte to achieve highly stable lithium metal batteries[J]. Adv Funct Mater, 2023, 33(27): 2300425.
[22]Tu M, Xia B, Kravchenko D E, et al. Direct X-ray and electron-beam lithography of halogenated zeolitic imidazolate frameworks[J]. Nat Mater, 2021, 20(1): 93-99.
[23]Jiang G, Qu C, Xu F, et al. Glassy metal-organic-framework-based quasi-solid-state electrolyte for high-performance lithium-metal batteries[J]. Adv Funct Mater, 2021, 31(43): 2104300.
[24]Xiang Y, Yu N, Li J, et al. Carving metal-organic-framework glass based solid-state electrolyte via a top-down strategy for lithium-metal battery[J]. Angew Chem Int Ed, 2025, 137(14): e202424288.
[25]Song X, Ma K, Wang J, et al. Three-dimensional metal-organic framework@cellulose skeleton-reinforced composite polymer electrolyte for all-solid-state lithium metal battery[J]. ACS Nano, 2024, 18(19): 12311-12324.
[26]Chen G, Jin B, Sun S, et al. Surface-functionalized metal-organic framework with high specific surface area optimizing composite solid electrolyte for high-performance solid-state lithium metal batteries[J]. Chem Eng J, 2024, 501: 157704.
[27]Zhou J, Wang X, Fu J, et al. A 3D cross-linked metal-organic framework (MOF)-derived polymer electrolyte for dendrite-free solid-state lithium-ion batteries[J]. Small, 2024, 20(18): 2309317.
[28]Liu H, Pan H, Yan M, et al. Extraordinary ionic conductivity excited by hierarchical ion-transport pathways in MOF-based quasi-solid electrolytes[J]. Adv Mater, 2023, 35(26): 2300888.
[29]Wu Z, Yi Y, Hai F, et al. A metal-organic framework based quasi-solid-state electrolyte enabling continuous ion transport for high-safety and high-energy-density lithium metal batteries[J]. ACS Appl Mater Interfaces, 2023, 15(18): 22065-22074.
[30]Li S, Chen Y, Leng X, et al. Rapid Li+ transport within the MOF-based composite solid electrolyte enables high-performance solid-state lithium-ion batteries[J]. Chem Eng J, 2024, 500: 157209.
[31]Xu M, Liang S, Shi H, et al. High-strength MOF-based polymer electrolytes with uniform ionic flow for lithium dendrite suppression[J]. Small, 2024, 20(46): 2406007.
[32]Li Z, Liu Q, Gao L, et al. Quasi-solid electrolyte membranes with percolated metal-organic frameworks for practical lithium-metal batteries[J]. J Energy Chem, 2021, 52: 354-360.
[33]Cui M, Zhao H, Qin Y, et al. Regulation of lithium-ion flux by nanotopology lithiophilic boron-oxygen dipole in solid polymer electrolytes for lithium-metal batteries[J]. Energy Environ Mater, 2024, 7(4): e12659.

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