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Published on: May 12, 2023
Tailoring the Electrochemical Properties of Two-Dimensional Bis(diimino)metal Coordination Frameworks by Introducing
Keisuke Wada1, Hiroaki Maeda1,2, Takuya Tsuji1
1Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Abstract:
Bis(diimino)metal coordination frameworks (MDI, M = transition metal), which are a class of metal organic frameworks with two-dimensional anisotropy, high electric conductivity, and redox activity, are attractive platforms for tailoring electrochemical properties by introducing a heterometallic composition. In this study, we synthesized heterometallic CoNi1-DI coordination frameworks for electrochemical energy storage applications and investigated their electrochemical properties by experimental and theoretical techniques. Ni atoms were embedded into CoDI, and the crystal structure of CoNi1-DI was modified, especially along the interlayer axis, which activated the kinetically impeded redox reactions accompanied by PF6- insertion/extraction. Furthermore, upon charge/discharge with Li+ transport, CoNi1-DI with a specific composition exhibited higher specific capacity (248 mAh g-1) than CoDI and NiDI in the potential window of 1.0-3.5 V versus Li+/Li. Density functional theory calculations indicate that the energy levels of the antibonding orbitals around the metals and interlayer spaces are important factors in tailoring the electrochemical properties of CoNi1-DI.
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