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1.4 Intercalation Chemistry

Intercalation is the insertion of atomic or molecular species into the structure of a host material.19 In layered materials, intercalation typically takes places where there is strong binding forces within a layer, but only weak interlayer binding forces. This behavior is prevalent in graphite, which is made up of sp2 bonded carbon layers separated by van der Waals gaps. While the covalently bonded carbon layers will not easily allow another atom or molecule to be inserted within the layer, species can easily be inserted between these layers. A schematic diagram of intercalation can be seen in Illustration 1.7.

Intercalation can be accomplished by a variety of methods.20 Vapor- phase intercalation can yield the highest quality materials since it is easier to separate the host from the species that is being inserted. This is often accomplished by placing the intercalation species at one end of a tube and the host at the other. This method requires that the intercalation species be volatile and stable enough at a given temperature to be transferred into the host lattice. Another method is to accomplish intercalation by a liquid or solution route. Exposing the host to the liquid of the intercalation species can be a rapid method of intercalation. Due to the rate of intercalation, this method can introduce a large number of defects into the host sample.

Schematic drawing of a layered material where a) is the lattice before intercalation, and b) is the lattice after intercalation of an atomic species such as K+ or Cs+.

Illustration 1.7: Schematic drawing of a layered material where a) is the lattice before intercalation, and b) is the lattice after intercalation of an atomic species such as K+ or Cs+.

While lowering the concentration by using a dilute solution of the intercalating species may overcome this problem, the intercalation of unwanted solvent molecules can occur. A solution method can also utilize electrochemical methods for intercalation. Finally, solid-phase reaction of an intercalation species can be employed. This method may exploit the application of pressure to facilitate intercalation. Removal of excess intercalation species could prove difficult. All three of these methods are usually carried out with an excess of intercalation species to insure the reaction goes to completion.

Three types of intercalation species can be inserted into the lattice of a host material. The first are electron donor species, which donate electrons to the lattice of the host material. Metals such as Li+, K+, and Hg+2 are typical donors that have been intercalated. Alloys of metals can also be intercalated. Next, acceptor species can also be intercalated. Iodine is a common acceptor used for intercalation. Vapor of I2 can enter a host lattice as I3-. Other examples of acceptors that can be used for intercalation are: Cl2, Br2, FeCl3, and MgCl2. Last of all neutral intercalation species can be intercalated. Benzene is one good example. Because there is not a strong driving force for the insertion of neutral species, only a small number of these have been intercalated. Often neutral species accompany donor or acceptor species from solution reactions.

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Updated on: April 15, 2010 8:26 PM