{"title":"Decoupling Interfacial Stability and Ion Transport in Solid Polymer Electrolyte by Tailored Ligand Chemistry for Lithium Metal Battery","authors":"Ruifan Lin, Yingmin Jin, Yumeng Li, Mengyu Fu, Yuxin Gong, Lei Lei, Yong Zhang, Jijian Xu, Yueping Xiong","doi":"10.1002/adfm.202421880","DOIUrl":null,"url":null,"abstract":"Achieving fast ion transport kinetics and high interfacial stability simultaneously is challenging for polymer electrolytes in solid-state lithium batteries, as the coordination environment optimal for Li<sup>+</sup> conduction struggles to generate desirable interphase chemistry. Herein, the adjustable property of organic ligands is exploited in metal–organic frameworks (MOFs) to develop a hierarchical composite electrolyte, incorporating heterogeneous and spatially confined MOF nanofillers into a poly-1,3-dioxolane matrix. The defect-engineered University of Oslo-66 MOFs (UiO-66d) with tailored Lewis acidity can separate ion pairs and optimize Li<sup>+</sup> migration through weakened solvation effects, thereby enhancing ion conductivity by over sixfold (0.85 mS cm<sup>−1</sup>@25 °C). At the lithium anode side, a densified University of Oslo-67 MOFs (UiO-67) layer with conjugated π electrons facilitates anion participation in the solvation sheath, promoting anion reduction and thereby forming LiF/Li<sub>3</sub>N-dominated solid electrolyte interphase for isotropic Li deposition. The as-assembled Li||LiFePO<sub>4</sub> full cell delivers superior cycling stability with 92.7% of capacity retained over 2000 cycles at 2 C. Notably, the developed electrolyte demonstrates excellent compatibility with high-voltage cathodes, achieving 80% capacity retention with LiNi<sub>0.5</sub>Co<sub>0.2</sub>Mn<sub>0.3</sub>O<sub>2</sub> over 630 cycles. This work provides valuable insights into decoupling transport and interfacial challenges in solid-state lithium batteries, paving the way for advanced battery technologies.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"70 1","pages":""},"PeriodicalIF":18.5000,"publicationDate":"2024-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Functional Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/adfm.202421880","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Achieving fast ion transport kinetics and high interfacial stability simultaneously is challenging for polymer electrolytes in solid-state lithium batteries, as the coordination environment optimal for Li+ conduction struggles to generate desirable interphase chemistry. Herein, the adjustable property of organic ligands is exploited in metal–organic frameworks (MOFs) to develop a hierarchical composite electrolyte, incorporating heterogeneous and spatially confined MOF nanofillers into a poly-1,3-dioxolane matrix. The defect-engineered University of Oslo-66 MOFs (UiO-66d) with tailored Lewis acidity can separate ion pairs and optimize Li+ migration through weakened solvation effects, thereby enhancing ion conductivity by over sixfold (0.85 mS cm−1@25 °C). At the lithium anode side, a densified University of Oslo-67 MOFs (UiO-67) layer with conjugated π electrons facilitates anion participation in the solvation sheath, promoting anion reduction and thereby forming LiF/Li3N-dominated solid electrolyte interphase for isotropic Li deposition. The as-assembled Li||LiFePO4 full cell delivers superior cycling stability with 92.7% of capacity retained over 2000 cycles at 2 C. Notably, the developed electrolyte demonstrates excellent compatibility with high-voltage cathodes, achieving 80% capacity retention with LiNi0.5Co0.2Mn0.3O2 over 630 cycles. This work provides valuable insights into decoupling transport and interfacial challenges in solid-state lithium batteries, paving the way for advanced battery technologies.
对于固态锂电池中的聚合物电解质来说,同时实现快速离子传输动力学和高界面稳定性是一个挑战,因为Li+传导的最佳配位环境难以产生理想的界面化学。本研究利用有机配体在金属-有机框架(MOF)中的可调特性,开发了一种层次化复合电解质,将非均相和空间受限的MOF纳米填料纳入聚1,3-二恶氧烷基体中。缺陷工程的奥斯陆大学66 mof (uuo -66d)具有量身定制的Lewis酸度,可以分离离子对并通过减弱溶剂化效应优化Li+迁移,从而将离子电导率提高六倍以上(0.85 mS cm - 1@25°C)。在锂阳极侧,致密的University of Oslo-67 mof (UiO-67)层具有共轭π电子,有利于阴离子参与溶剂化鞘,促进阴离子还原,从而形成以LiF/ li3n为主的固体电解质界面,用于各向同性锂沉积。组装后的Li||LiFePO4全电池具有优异的循环稳定性,在2℃下循环2000次,容量保留率为92.7%。值得注意的是,所开发的电解质与高压阴极具有良好的兼容性,在630次循环中,LiNi0.5Co0.2Mn0.3O2的容量保留率达到80%。这项工作为固态锂电池的解耦传输和界面挑战提供了有价值的见解,为先进的电池技术铺平了道路。
期刊介绍:
Firmly established as a top-tier materials science journal, Advanced Functional Materials reports breakthrough research in all aspects of materials science, including nanotechnology, chemistry, physics, and biology every week.
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