Graphite intercalation into

The formation of fullerenes and CNTs has also been affected by their environmental atmosphere [22] and, in particular, a hydrogen atmosphere plays an important role in forming graphitic structures of multi-walled CNTs (MWCNTs) in the form of buckybundles [24]. Intercalation into MWCNTs has been difficult or impossible, because there is no space for intercalants to enter into a Russian-doll-type structure of the nanotubes. However, the buckybundles formed in the hydrogen arc discharge were found to be successfully intercalated with potassium and ferric chloride (FeCl3) without breaking the... 

Storage in inorganic solid matrix Intercalation into graphite [6,7] Carbon-bromine adduct [4] In zeolites [8]... 

Numerous research activities have focused on the improvement of the protective films and the suppression of solvent cointercalation. Beside ethylene carbonate, significant improvements have been achieved with other film-forming electrolyte components such as C02 [156, 169-177], N20 [170, 177], S02 [155, 169, 177-179], S/ [170, 177, 180, 181], ethyl propyl carbonate [182], ethyl methyl carbonate [183, 184], and other asymmetric alkyl methyl carbonates [185], vinylpropylene carbonate [186], ethylene sulfite [187], S,S-dialkyl dithiocarbonates [188], vinylene carbonate [189], and chloroethylene carbonate [190-194] (which evolves C02 during reduction [195]). In many cases the suppression of solvent co-intercalation is due to the fact that the electrolyte components form effective SEI films already at potential which are positive relative to the potentials of solvent co-intercalation. An excess of DMC or DEC in the electrolyte inhibits PC co-intercalation into graphite, too [183]. 

Using dilatometry in parallel with cyclic voltammetry (CV) measurements in lmolL 1 LiC104 EC-l,2-dimethoxy-ethane (DME), Besenhard et al. [87] found that over the voltage range of about 0.8-0.3 V (vs. Li/Li+), the HOPG crystal expands by up to 150 percent. Some of this expansion seems to be reversible, as up to 50 percent contraction due to partial deintercalation of solvated lithium cations was observed on the return step of the CV. It was concluded [87] that film formation occurs via chemical reduction of a solvated graphite intercalation compound (GIC) and that the permselective film (SEI) in fact penetrates into the bulk of the HOPG. It is important to repeat the tests conducted by Besenhard et al. [87] in other EC-based electrolytes in order to determine the severity of this phenomenon. 

The smaller ion may intercalate faster into the graphite galleries. Reaction (5) may be the rate-determining step for the solvent co-intercalation process, and if so, molecules that form large and stable solvated lithium cations will have a smaller tendency for co-intercalation into the graphite. 

Of the chlorine fluorides, only the monofluoride does not intercalate in the neat state. It does, however, intercalate in the presence of HF (S15), BF3, or PFj (S16). Chlorine trifluoride intercalates into graphite with simultaneous fluorination of the graphite lattice (Si5), releasing... 

At this time, no all-inclusive rule can be given that will predict whether a given compound will intercalate or not. Most of the information available seems to have been obtained empirically. Such analogies as similar chemical properties have been helpful. The many factors that infiuence the intercalation process have been surveyed by Herold (H14). In Tables II-VI are listed metal halides considered to intercalate into graphite, together with some structural information (S2J, i 9). Several general characteristics have been ascribed to intercalat-... 

At the end of the 1990s in Japan, large-scale production of rechargeable lithium ion batteries was initiated. These contained lithium compounds intercalated into oxide materials (positive electrodes) as well as into graphitic materials (negative electrode). The development of these batteries initiated a further increase in investigations of the properties of different intercalation compounds and of the mechanism of intercalation and deintercalation processes. 

The electrochemical intercalation into graphite leads in the most simple case to binary compounds (graphite salts) according to the schematic equations ... 

Figure 4. Depiction of lithium intercalated into the carbon/graphite lattice.

When the electrolyte solutions are not too reactive, as in the case of ethereal solutions, there is no massive formation of protective surface films at potentials above Li intercalation potential, and most of the solvent reduction processes may occur at potentials lower than 0.3 V vs. Li/Li+. Hence, the passivation of the electrodes is not sufficient to prevent cointercalation of solvent molecules. This leads to an exfoliation of the graphite particles into amorphous dust (expholiated graphene planes). This scenario is demonstrated in Figure 2a as the reduction of the 002 diffraction peak21 of the graphite electrode, polarized cathodically in an ethereal solution. 

Figure 6. The entropy of lithium intercalation into natural graphite, after [22],...

For a number of reasons the TiS2 battery was not widely exploited commercially, but similar batteries based upon intercalation into transition-metal oxides LiJCTO2, where T is a 3d transition metal such as Ni, Co, or Mn (or a solid solution of these metals, LiJt.T1 yTj,02) are widely available. The first of these, the Sony cell, introduced in 1991, employs LixCo02 as the cathode and the intercalation of Li into graphite as the anode, to form LivC6. 

It has been known for some time that lithium can be intercalated between the carbon layers in graphite by chemical reaction at a high temperature. Mori et al. (1989) have reported that lithium can be electrochemically intercalated into carbon formed by thermal decomposition to form LiCg. Sony has used the carbon from the thermal decomposition of polymers such as furfuryl alcohol resin. In Fig. 11.23, the discharge curve for a cylindrical cell with the dimensions (f) 20 mm x 50 mm is shown, where the current is 0.2 A. The energy density for a cutoff voltage of 3.7 V is 219 W h 1 which is about two times higher than that of Ni-Cd cells. The capacity loss with cycle number is only 30% after 1200 cycles. This is not a lithium battery in the spirit of those described in Section 11.2. 

In a subject with the breadth of solid state electrochemistry, and with the inevitable constraints on the length of a textbook, some topics have been omitted. In particular, less emphasis on proton conduction has been given than on the transport of other ions, in part because of the existence of a recent book on this topic in the same series. Proton Conductors, Ed. Philippe Colomban, Cambridge University Press (1992). Also the important topic of intercalation into graphite has been largely omitted. Several excellent texts on this subject are already available. 

Figure 1. Schematic description of a (lithium ion) rocking-chair cell that employs graphitic carbon as anode and transition metal oxide as cathode. The undergoing electrochemical process is lithium ion deintercalation from the graphene structure of the anode and simultaneous intercalation into the layered structure of the metal oxide cathode. For the cell, this process is discharge, since the reaction is spontaneous.

Figure 11. (a) Initial IV2 cycles of a Li/petroleum coke cell. The cell was cycled at a rate of 12.5 h for Ax = 0.5 in Li sG6. (b) Initial IV2 cycles of a Li/graphite cell. The cell was cycled at a rate of 40 h for Ax= 0.5 in Li sG6. F denotes the irreversible capacity associated with SEI formation, E the irreversible capacity due to exfoliation, and I the reversible capacity due to lithium intercalation into carbon. 1.0 M LiAsEe in EC/PC was used as electrolyte. (Reproduced with permission from ref 36 (Eigure 2). Copyright 1990 The Electrochemical Society.)... 

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