NOVEL GRAPHITE INTERCALATION COMPOUNDS CONTAINING FLUORINE, THEIR PROPERTIES AND MANIFESTATION OF FUNCTIONALITY.

1.氟-石墨插层化合物C_xF随着反应温度的降低而增加，在低温范围（RT - -78 C）下反应时间长（14-140天）可形成成分范围宽（3<x<13）的C_xF。在SbF_3或HF存在下的插层速率比在纯氟存在下的插层速率快得多，反应时间短于7天，形成C_xF （3<x<13）。氟含量低于x=6的C_xF的插层厚度d_i为2.7 A^^，说明插层物质为氟离子，位于石墨廊的中间。当氟含量超过C_6F时，C-F键的性质由离子型转变为半离子型，二级C_xF的同质周期I_c变为10.6 A^^。这表明插层的氟原子不在石墨层中间。C_xF的sigma_<ab>值随着氟含量的增加而增大，在x=8.4时达到最大值（sigma_<ab> = 2.25 × 10^5 S/cm）。其最大值约为原始石墨晶体的10倍。在达到最大值后，sigma_<ab>随氟含量的增加而减小，具有半离子型C-F键的富氟C_xF （x<3）由于半离子型C-F键形成的pi电子局域化，几乎是绝缘体。通过对二级化合物C_<6.1>F的反射光谱定性分析，推导出其部分物理性质。费米能量为0.72 eV，碳原子和氟原子的电荷转移量分别为0.01和0.07。一级氟化砷酸石墨的有序-无序转变。第1阶段石墨氟砷酸盐插层化合物C_<16>AsF_6的ginier - simon x射线衍射结果表明，该化合物在约170 K的温度下发生了有序-无序转变，并且在低温阶段，AsF_6^-阴离子的f配体坐落在封闭石墨层的连续三层碳原子六边形中，阴离子呈三维有序排列。少

1.Fluorine-Graphite Intercalation Compounds C_xF The rate of fluorine intercalation increases with decreasing reaction temperature, and C_xF with the wide composition range (3<x<13) are formed by long reaction times (14-140 days) at a low temperature range (RT - -78ﾟC). The rate of intercalation in the presence of SbF_3 or HF is much faster then that of pure fluorine, and C_xF (3<x<13) are formed by a shorter reaction time than 7 days.2.Structure of C_xF and Nature of C-F bond The intercalate thickness d_i of C_xF with lower fluorine content than x=6 is 2.7 A^^ﾟ, indicating that intercalated species are fluoride ion and are in the midway between graphite galleries. When the fluorine content exceeds that of C_6F, the nature of C-F bond varies from ionic to semi-ionic and the identity period I_c of stage-2 C_xF becomes 10.6 A^^ﾟ. This suggests that intercalated fluorine atoms are not in the midway between graphite galleries.3.Charge Transfer and In-Plane Electrical Conductivity sigma_<ab … More > Values of sigma_<ab> of C_xF increase with increasing fluorine content and show the maximum (sigma_<ab> = 2.25x10^5 S/cm) at x=8.4. The maximum value is ca. 10 times higher than that of pristine graphite crystal. After the maximum, sigma_<ab> decrease with increasing fluorine content and the fluorine-rich C_xF (x<3) with semi-ionic C-F bond are almost insulators because of pi-electron localization by the semi-ionic C-F bond formation. The some physical properties are deduced by the qualitative analysis of reflectance spectra for stage-2 compound C_<6.1>F. The fermi energy is 0.72 eV, and the charge transfer per carbon atom and the charge transfer per fluorine atom are 0.01 and 0.07, respectively.4.The Order-Disorder Transition of Stage-1 Graphite Fluoroarsenate. Guinier-Simon X-ray diffraction date for the stage-1 graphite fluoroarsenate intercalation compound, C_<16>AsF_6, indicate that it undergoes an order-disorder transition at ca. 170 K and has the F-ligands of AsF_6^- anions nestled in contiguous three-fold sets of carbon-atom hexagons of the enclosing graphite layers with 3-dimensional ordering of the anions in the low temperature phase. Less