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Fluorine or Fluoride-Graphite Intercalation Compounds as New Electroconductive Materials

作为新型导电材料的氟或氟化物-石墨插层化合物

基本信息

批准号：
62550586
负责人：
NAKAJIMA Tsuyoshi
金额：
$ 1.15万
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：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

The structures, chemical bond and electrical conductivities have been investigated on titanium fluoride, vanadium fluoride, niobium fluoride or tantalum fluoride-graphite intercalation compound prepared in fluorine atmosphere. Titanium fluoride and vanadium fluoride gave mainly stage 2 compounds in which fluoride is inserted in every other layer of graphite, however, niobium fluoride and tantalum fluoride easily produce the stage 1 in which fluoride is inserted in every graphite layer. Elemental analysis, XPS and X-ray diffraction have indicated that titanium fluoride takes a bridged chain structure in which TiF^2-_ share fluoride ions, and vanadium fluoride anion easily gets into the hexagons of graphite layer(nestling). These structures give high stagility to the compounds by preventing diffusion of hexa-fluoroanion between graphite layers. On the other hand, the nestling of NbF^-_ and TaF^-_ is difficult because they have larger cations than vanadium ion. The compounds of NbF^-_ and TaF^-_ are therefore unstagle. XPS has also shown that the host graphite and intercalated fluoride has ionic bond.The electrical conductivities of these compounds have been measured by contact -less Wien bridge. The conductivities were 1.7-2.0x10^5 Scm^<-1>, being 10-12 times that of pristine graphite(HOPG, highly oriented pyrolytic graphite).Especially those for titanium fluoride or vanadium fluoride intercalated graphite were almost unchanged for several to 8 months in air.

研究了在氟气氛下制备的氟化钛、氟化钒、氟化铌和氟化钽-石墨层间化合物的结构、化学键和导电性。氟化钛和氟化钒主要产生其中氟化物插入到石墨的每隔一层中的第2阶段化合物，然而，氟化铌和氟化钽容易产生其中氟化物插入到每个石墨层中的第1阶段化合物。元素分析、X射线光电子能谱和X射线衍射分析表明，氟化钛为桥联结构，其中TiF_2 ~（2-）共享氟离子，氟化钒阴离子易进入石墨层的六边形结构中（雏型）。这些结构通过防止六氟阴离子在石墨层之间扩散而赋予化合物高稳定性。另一方面，NbF^-_和TaF^-_的嵌套是困难的，因为它们具有比钒离子大的阳离子。因此NbF^-_和TaF^-_的化合物是不稳定的。XPS分析表明，主体石墨与插层氟化物之间存在离子键，用非接触式维恩电桥测量了这些化合物的电导率。导电率为1.7- 2.0 × 10 ~（-5）Scm ~<-1>（-1），是原始石墨（HOPG）的10-12倍，特别是氟化钛和氟化钒插层石墨，在空气中放置几个月至8个月，其导电率几乎不变。