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Preparation and Properties of Fluoride-Graphite Intercalation Compounds with Different Oxidation Number of Intercalant

不同插层剂氧化数氟化石墨插层化合物的制备及性能

基本信息

批准号：
60550552
负责人：
TOUHARA Hidekazu
金额：
$ 0.64万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1986
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-60550552/
关键词：
Graphite Intercalation Compound Fluorine Fluoride Conductivity リチウム電池

项目摘要

Fluoride-graphite intercalation compounds(GICs) were prepared as follows, 1) <C_x(SbF_5)_n(SbF_6^-)_(1-n)> : reactions(0-200゜C) of graphite with <SbF_3> under one atmosphere fluorine pressure, 2) involatile fluoride based-GICs( <C_xSnF_y> , <C_xPbF_y> , <C_xBiF_y> ) : reactions(15゜C) of graphite with involatile fluorides dissolved in liquid HF under <F_2> bubbling, 3) fluorine-GICs( <C_xF> ) : reactions(20-200゜C) of graphite fibers and activated carbon fibers with one atmosphere <F_2> gas. The oxidation number of GICs <C_xMF_y> are + <III> , + <IV> and + <V> , which depends on preparative method and starting fluorides. The nature of C-F bond in <C_xF> varies from chemisorption to complete covalent bond depending on reaction temperature. <C_x(SbF_5)_n(SbF_6^-)_(1-n)> and <C_xSnF_y> show high in-plane electrical conductivity( <about> <10^5> S <cm^(-1)> and <C_xF> are semi-conductor or insulator.Electrochemical characteristics of GICs as a cathode material of lithium batteries were investigated by cells Li/1M <LiClO_4-PC/C_xMF_y> , <C_xF> . The <C_xSnF_y> cathode give very high open circuit voltage(OCV) ranging from 3.9 to 4.2 V, however overpotentials are considerably high and the discharge potentials at 0.1 mA/ <cm^2> are 1.2-2.5 V with cathode utility more than 80%. OCVs of <C_xF> cathodes are 3.6-3.7 V and discharge potentials at 0.5 mA/ <cm^2> are ca. 2.5 V with cathode utility ca. 80%. A certain extent of three dimensional structure of <C_xF> is required to be a cathode material with high performances.

氟化物-石墨插层化合物（GIC）的制备如下，1）<C_x（SbF_5）_n（SbF_6^-）_（1-n）>：石墨与<SbF_3>在大气压氟压下反应（0-200゜C），2）不挥发性氟化物基-GIC（<C_xSnF_y>， <C_xPbF_y> , <C_xBiF_y> ) : 在 <F_2> 鼓泡下石墨与溶解在液体 HF 中的不挥发性氟化物的反应(15゜C)，3) 氟-GIC( <C_xF> ) : 石墨纤维和活性碳纤维在<F_2>气氛下的反应(20-200゜C)。 GIC <C_xMF_y> 的氧化数为 + <III> 、 + <IV> 和 + <V> ，这取决于制备方法和起始氟化物。 <C_xF> 中 C-F 键的性质根据反应温度从化学吸附到完全共价键变化。 <C_x(SbF_5)_n(SbF_6^-)_(1-n)>和<C_xSnF_y>表现出高面内电导率（<about><10^5>S<cm^(-1)>和<C_xF>是半导体或绝缘体。通过电池研究了GIC作为锂电池正极材料的电化学特性 Li/1M <LiClO_4-PC/C_xMF_y> , <C_xF> 。 <C_xSnF_y> 阴极提供非常高的开路电压 (OCV)，范围为 3.9 至 4.2 V，但过电势相当高，0.1 mA/ <cm^2> 时的放电电势为 1.2-2.5 V，阴极利用率超过 80%。 <C_xF> 的 OCV 阴极电压为 3.6-3.7 V，0.5 mA/ <cm^2> 时的放电电势约为2.5 V，带阴极实用程序约。 80%。需要<C_xF>具有一定程度的三维结构才能成为高性能的正极材料。