研究了熔融盐状态下金属氯化物-石墨层间化合物的合成判据.根据插层反应热动力学及化学键理论,选取元素的电负性和离子势作为键参数,并设计键参数函数λ为客体材料的遴选判据.基于键参数函数图对金属氯化物发生插层反应的难易程度和产物稳定性进行理论预估.研究结果表明:键参数函数图中λ≤1.2区域内的金属氯化物在700℃以下即可发生插层反应,且所得产物较为稳定;在1.2≤λ≤1.8区域内相应的客体材料在低温下很难单独插入石墨层间,常与低熔点氯化物形成共熔体后一起插入石墨层间;在λ≥1.8区域内大多为碱金属氯化物和碱土金属氯化物,理论分析认为这类物质的插层反应不适宜采用熔盐法.
A criterion for the intercalation of a metal chloride in a molten state into graphite was proposed based on the thermodynamics of the intercalation reaction and chemical band theory, The valence electronegativity of element and ionic potential are taken as the chemical band parameters and a band parameter function λ is defined as a criterion to select a guest metal chloride to prepare a graphite intercalation compound (GIC). The ability of a metal chloride to be intercalated into graphite and the stability of the resulting GIC are estimated. The results show that GICs synthesized at a temperature lower than 700℃ are more stable when a metal chloride is chosen from the region of λ≤1.2. A metal chloride with λ between 1.2 and 1.8 cannot be easily intercalated into graphite alone. The metal chlorides with λ≥1.8, most of which are alkaline earth chlorides or alkali metal chlorides, are not appropriate as guests to prepare G1Cs by a molten salt method. The criterion is consistent with the experimental data and some new expected results are also obtained.
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