Toyota Central R&D Laboratories, Inc. , 41-1 Yokomichi , Nagakute , Aichi 480-1192 , Japan.
Department of Chemistry , Fukuoka University , Jonan-ku, Fukuoka 810-0180 , Japan.
Inorg Chem. 2019 Feb 18;58(4):2379-2385. doi: 10.1021/acs.inorgchem.8b02768. Epub 2019 Feb 7.
Host-guest materials based on coordination polymers (CPs) are currently emerging as potential candidates for battery applications. In this context, we describe the preparation of three-dimensional network structures containing BF anions and water molecules in the one-dimensional (1D) channels via hydrothermal reactions between Cu(BF) and 4,4'-bipyridine or 1,2-di-4-pyridylethylene. A systematic characterization of the obtained CPs using single-crystal X-ray diffraction, X-ray absorption fine structure, and an electrochemical test was performed. The results showed that the BF anions were electrochemically reduced to BF in the cavities of the CPs, with concomitant elimination of a leaving fluoride at room temperature. Using this electrochemical property, a prototype battery, in which the CPs act as the anode and graphite as the cathode, was demonstrated. The cell exhibited a practical discharge potential of ∼1.5 V. This constitutes the first demonstration of CPs showing electrochemical B-F bond activation in the 1D channels and rocking-chair-type fluoride insertion and extraction by changes in the electric potential.
基于配位聚合物（CPs）的主客体材料目前作为电池应用的潜在候选材料而崭露头角。在这种情况下，我们通过 Cu（BF）与 4,4'-联吡啶或 1,2-二（4-吡啶基）乙烯之间的水热反应，描述了在一维（1D）通道中含有 BF 阴离子和水分子的三维网络结构的制备。使用单晶 X 射线衍射、X 射线吸收精细结构和电化学测试对获得的 CPs 进行了系统的表征。结果表明，BF 阴离子在 CPs 的腔室中被电化学还原为 BF，同时在室温下消除了离去的氟化物。利用这种电化学性质，演示了一种以 CPs 为阳极、石墨为阴极的原型电池。该电池表现出约 1.5 V 的实用放电电位。这首次证明了 CPs 在 1D 通道中表现出电化学 B-F 键活化，以及通过电势变化进行摇椅式氟化物插入和提取。
