Synthetic Metals, 7 (1983) 107 - 115 107
INTERCALATE DISPLACEMENT AND EXCHANGE IN GRAPHITE*
S. H. ANDERSON and D. D. L. CHUNG
Department of Metallurgical Engineering and Materials Science, Carnegie-Mellon Uni-
versity, Pittsburgh, PA 15213 (U.S.A.)
Summary
The mechanism of intercalate transport in graphite was studied by
sequential intercalation of bromine and iodine monochloride. It was found
that the transport involved solid-state intercalate displacement such that the
first intercalate molecule to enter an interlayer space is the first to reach the
center of the graphite sample. Upon exposure of stage-2 graphite-bromine to
IC1, the in-plane superlattice diffraction pattern was observed to change from
that of graphite-bromine to that of graphite-IC1, while the IC1 intercalate
distributed itself uniformly at a concentration level above that of the bromine
intercalate. This is interpreted as the expulsion of bromine by the in-coming
IC1, which dissolved the remaining bromine to form a solid solution with the
ICl in-plane structure.
1. Introduction
The question of intercalate transport is important from a technological
viewpoint. In batteries, for example, intercalate transport would have a direct
bearing on the cell current. Intercalate transport also must be considered in
replacement or exchange reactions where the first intercalation compound to
be formed is an intermediate to the final compound. Examples of replace-
ment reactions include the formation of transition metal intercalation com-
pounds from alkali metal intercalation compounds [1], and the reaction of
aluminum bromide with residue graphite-bromine compounds [ 2].
The keynote of work pertaining to the mechanism of intercalate trans-
port is Hooley's [3, 4] observation that intercalation begins at the basal edges
adjacent to basal surfaces, and that the intercalating species migrate between
*Research sponsored by the Air Force Office of Scientific Research, Air Force
Systems Command, USAF, under Grant No. AFOSR-78-3536. The United States Govern-
ment is authorized to reproduce and distribute reprints for governmental purposes not-
withstanding any copyright notation hereon.
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