Intercalation, of carbon

Towards the northwest and in the extreme north the proportion of sandstones and siltstones in the succession decreases and intercalations of carbonates, mostly argillaceous sandstones, make their appearance. These sediments formed in a shallow sea. They accumulated under deeper water than those in the north. According to the adsorbed complex the salinity of the Silurian sea must have been low, probably because of the melting of the glaciers which led to a reduction of the salinity of the basin waters. The basin was not deeper than about 200 m. 

Intercalation of carbon fibers The crystal structure of graphite is of a kind that permits the formation of many compounds, called lamellar or intercalation compounds, by insertion of molecules or ions between the graphitic layers. 

Carbon fibers can react to form intercalation compounds when the reactant (intercalate) enters between the graphite layer planes, forcing them apart. Although the layer planes are pushed apart, the distance between the carbon atoms within a sheet remains unaltered. Hence the volume of carbon fiber per unit volume is reduced and the resistivity is decreased. Intercalation is generally restricted to carbon fibers with a graphitic structure. Typical intercalates are Br2, liquid K and FeCla. Tressaud et al [199] have reported the intercalation of carbon fibers with fluorine. 

Graphite reacts with alkali metals, for example potassium, to form compounds which are non-stoichiometric but which all have limiting compositions (for example K C) in these, the alkaU metal atoms are intercalated between the layers of carbon atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite electrodes the solid compound (CF) polycarbon fluoride is formed, with fluorine on each carbon atom, causing puckering of the rings. 

Further improvements in anode performance have been achieved through the inclusion of certain metal salts in the electrolyte, and more recently by dkect incorporation into the anode (92,96,97). Good anode performance has been shown to depend on the formation of carbon—fluorine intercalation compounds at the electrode surface (98). These intercalation compounds resist further oxidation by fluorine to form (CF ), have good electrical conductivity, and are wet by the electrolyte. The presence of certain metals enhance the formation of the intercalation compounds. Lithium, aluminum, or nickel fluoride appear to be the best salts for this purpose (92,98). 

Graphitic carbon is now used as the anode material in lithium-ion batteries produced by Moli Energy (1990) Ltd., Matsushita, Sanyo and A+T battery. It is important to understand how the structures and properties of graphitic carbons affect the intercalation of lithium within them. 

Carbon materials which have the closest-packed hexagonal structures are used as the negative electrode for lithium-ion batteries carbon atoms on the (0 0 2) plane are linked by conjugated bonds, and these planes (graphite planes) are layered. The layer interdistance is more than 3.35 A and lithium ions can be intercalated and dein-tercalated. As the potential of carbon materials with intercalated lithium ions is low,... 

A. H rold, Crystallo-chemistry of carbon intercalation compounds, in Intercalated Materials (Ed. F. Levy), D. Reidel, Dordrecht,... 

In redox flow batteries such as Zn/Cl2 and Zn/Br2, carbon plays a major role in the positive electrode where reactions involving Cl2 and Br2 occur. In these types of batteries, graphite is used as the bipolar separator, and a thin layer of high-surface-area carbon serves as an electrocatalyst. Two potential problems with carbon in redox flow batteries are (i) slow oxidation of carbon and (ii) intercalation of halogen molecules, particularly Br2 in graphite electrodes. The reversible redox potentials for the Cl2 and Br2 reactions [Eq. (8) and... 

The quality and quantity of sites which are capable of reversible lithium accommodation depend in a complex manner on the crystallinity, the texture, the (mi-cro)structure, and the (micro)morphology of the carbonaceous host material [7, 19, 22, 40-57]. The type of carbon determines the current/potential characteristics of the electrochemical intercalation reaction and also potential side-reactions. Carbonaceous materials suitable for lithium intercalation are commercially available in many types and qualities [19, 43, 58-61], Many exotic carbons have been specially synthesized on a laboratory scale by pyrolysis of various precursors, e.g., carbons with a remarkably high lithium storage capacity (see Secs. 

Staging phenomena as well as the degree of intercalation can be easily observed during the electrochemical reduction of carbons in Li+-containing electrolytes. Figure 6 (left) shows a schematic poten-tial/composition curve for the galvanostatic... 

Whereas the electrochemical decomposition of propylene carbonate (PC) on graphite electrodes at potentials between 1 and 0.8 V vs. Li/Li was already reported in 1970 [140], it took about four years to find out that this reaction is accompanied by a partially reversible electrochemical intercalation of solvated lithium ions, Li (solv)y, into the graphite host [64], In general, the intercalation of Li (and other alkali-metal) ions from electrolytes with organic donor solvents into fairly crystalline graphitic carbons quite often yields solvated (ternary) lithiated graphites, Li r(solv)yC 1 (Fig. 8) [7,24,26,65,66,141-146],... 

Apart from reactions with the electrolyte at the carbon surface, the irreversible specific charge is furthermore strongly affected by the possible co-intercalation of polar solvent molecules between the graphene layers of highly graphitic matrices [139]. This so-called "solvated intercalation reaction" depends (i) on the crystallinity and the morphology of the parent carbonaceous material, which will be discussed in Sec. 

One of the most important factors affecting Qsei [76, 78, 87] is graphite-anode exfoliation, as a result of intercalation of solvated lithium ions. Factors that are reported to decrease (9lR are increasing the EC content in organic carbonates or di-oxolane solutions [98, 991 addition of C02 [31, 87, 99] or crown ethers [8, 71, 78] and increasing the current density [73] (this also lowers <2SE [14] as a result of decrease in (2s P ) ... 

The chemical composition of the SEI formed on carbonaceous anodes is, in general, similar to that formed on metallic lithium or inert electrodes. However some differences are expected as a result of the variety of chemical compositions and morphologies of carbon surfaces, each of which can affect the i() value for the various reduction reactions differently. Another factor, when dealing with graphite, is solvent co-intercalation. Assuming Li2C03 to be a major SEI building material, the thickness of the SEI was estimated to be about 45 A [711. 

Because of the reactivity of lithium or lithium intercalated in carbon, protic solvents cannot be used in lithium batteries because hydrogen would be formed according to Eq. (1). 

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