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克服 Faradaic 过程的扩散限制:二维导电金属有机骨架 Cu(HHTP)用于可逆锂离子存储的性能-关系。

Overcoming Diffusion Limitation of Faradaic Processes: Property-Performance Relationships of 2D Conductive Metal-Organic Framework Cu (HHTP) for Reversible Lithium-Ion Storage.

机构信息

University of Münster, MEET Battery Research Center, Corrensstraße 46, 48149, Münster, Germany.

Helmholtz-Zentrum Berlin für Materialien und Energie GmbH (HZB), Albert-Einstein-Straße 15, 12489, Berlin, Germany.

出版信息

Angew Chem Int Ed Engl. 2023 Jun 26;62(26):e202303111. doi: 10.1002/anie.202303111. Epub 2023 May 17.

Abstract

Faradaic reactions including charge transfer are often accompanied with diffusion limitation inside the bulk. Conductive two-dimensional frameworks (2D MOFs) with a fast ion transport can combine both-charge transfer and fast diffusion inside their porous structure. To study remaining diffusion limitations caused by particle morphology, different synthesis routes of Cu-2,3,6,7,10,11-hexahydroxytriphenylene (Cu (HHTP) ), a copper-based 2D MOF, are used to obtain flake- and rod-like MOF particles. Both morphologies are systematically characterized and evaluated for redox-active Li ion storage. The redox mechanism is investigated by means of X-ray absorption spectroscopy, FTIR spectroscopy and in situ XRD. Both types are compared regarding kinetic properties for Li ion storage via cyclic voltammetry and impedance spectroscopy. A significant influence of particle morphology for 2D MOFs on kinetic aspects of electrochemical Li ion storage can be observed. This study opens the path for optimization of redox active porous structures to overcome diffusion limitations of Faradaic processes.

摘要

包括电荷转移的法拉第反应通常伴随着体相中的扩散限制。具有快速离子传输能力的导电二维框架(2D MOFs)可以在其多孔结构内结合电荷转移和快速扩散。为了研究由于颗粒形态引起的剩余扩散限制,使用不同的合成路线来获得片状和棒状 MOF 颗粒,以得到基于铜的 2D MOF-铜-2,3,6,7,10,11-六羟基三苯(Cu(HHTP)。对这两种形态进行了系统的表征,并评估了它们在氧化还原活性锂离子存储方面的性能。通过 X 射线吸收光谱、傅里叶变换红外光谱和原位 XRD 研究了氧化还原机理。通过循环伏安法和阻抗谱比较了这两种类型在锂离子存储方面的动力学性质。可以观察到 2D MOF 的颗粒形态对电化学锂离子存储的动力学方面有显著影响。这项研究为优化氧化还原活性多孔结构以克服法拉第过程的扩散限制开辟了道路。

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