Deintercalation

The first 1.5 charge-discharge cycles of lithium/carbon cells are presented in Fig. 4 for both graphite (b) and petroleum coke (a) [71], In both cases, the first intercalation capacity is larger than the first deintercalation capacity. 

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. 

From these results there is evidence that it is possible to vise well-defined graphite intercalates as precursors for deliberate deintercalation, yielding a multiphasic supported material which is catalytically active. 

Apart from the work toward practical lithium batteries, two new areas of theoretical electrochemistry research were initiated in this context. The first is the mechanism of passivation of highly active metals (such as lithium) in solutions involving organic solvents and strong inorganic oxidizers (such as thionyl chloride). The creation of lithium power sources has only been possible because of the specific character of lithium passivation. The second area is the thermodynamics, mechanism, and kinetics of electrochemical incorporation (intercalation and deintercalation) of various ions into matrix structures of various solid compounds. In most lithium power sources, such processes occur at the positive electrode, but in some of them they occur at the negative electrode as well. 

Detailed studies have been performed on pseudocapacitors with layers of hydrated ruthenium oxide, RuOj- HjO. Protons relatively readily undergo intercalation and deintercalation in this material ... 

A wider application of ruthenium oxide capacitors is hindered by the high cost of ruthenium oxide. Attempts have been reported, therefore, to substitute ruthenium oxide with other, cheaper materials capable of intercalation and deintercalation of hydrogen and/or other ions. Promising results with pseudocapacities of about 100 F/g have been obtained with the mixed oxides of ruthenium and vanadium and also with mixed oxides on the basis of manganese oxide. 

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. 

Different investigations of the mechanisms of capacity degradation during cycling show that one of the main reasons of this degradation is significant change (by a factor of 3-4) in AM volume on the intercalation-deintercalation of lithium, followed by AM destruction [2-3],... 

Both carbon materials were tested for their initial electrochemical performance in the 2-electrode electrochemical cells with Li metal as a counter electrode. Our findings have shown that with both types of carbon materials, achieving near theoretical reversible capacity upon Li+ deintercalation was possible. Thus, in a typical half cell environment (a CR2016 type coin cell with graphite and Li metal electrodes, a 1M LiPF6,... 

Forsman W.C., Mertwoy H.E., Wessbecher D.E. Nonreductive spontaneous deintercalation of graphite nitrate. Carbon 1988 26 693-699. 

This may lead to the irreversible changes in the material, caused by partial oxidation of graphite, loss of reversibility of the system along with the efficiency of reaction for intercalation-deintercalation (1). 

When cycling a NGF electrode under the same conditions (Figure 2), the deintercalation peak current values are much higher. At the same time, under comparable conditions, a noticeable surface oxidation of NGF starts to be observed significantly earlier, after Nstable = 50-60 cycles. The service life of the NGF electrode is Nmax =100 cycles. 

Chemical relaxation methods can be used to determine mechanisms of reactions of ions at the mineral/water interface. In this paper, a review of chemical relaxation studies of adsorption/desorption kinetics of inorganic ions at the metal oxide/aqueous interface is presented. Plausible mechanisms based on the triple layer surface complexation model are discussed. Relaxation kinetic studies of the intercalation/ deintercalation of organic and inorganic ions in layered, cage-structured, and channel-structured minerals are also reviewed. In the intercalation studies, plausible mechanisms based on ion-exchange and adsorption/desorption reactions are presented steric and chemical properties of the solute and interlayered compounds are shown to influence the reaction rates. We also discuss the elementary reaction steps which are important in the stereoselective and reactive properties of interlayered compounds. 

The fast reactions of ions between aqueous and mineral phases have been studied extensively in a variety of fields including colloidal chemistry, geochemistry, environmental engineering, soil science, and catalysis (1-6). Various experimental approaches and techniques have been utilized to address the questions of interest in any given field as this volume exemplifies. Recently, chemical relaxation techniques have been applied to study the kinetics of interaction of ions with minerals in aqueous suspension (2). These methods allow mechanistic information to be obtained for elementary processes which occur rapidly, e.g., for processes which occur within seconds to as fast as nanoseconds (j0. Many important phenomena can be studied including adsorption/desorption reactions of ions at electri fied interfaces and intercalation/deintercalation of ions with minerals having unique interlayer structure. 

Ag VjOj is a vanadium bronze with a composition range of 0.3 < x < 1.0, the bronze with x = 0.29-0.41 has the / -phase structure and that with X = 0.67-0.89 the 5-phase one. The 5-phase shows good reversibility for silver intercalation and deintercalation. The typical charge-discharge curves at a constant current of 0.3 mA cm for cell [11.3] are shown in Fig. 11.3. No significant deterioration was observed for several hundred... 

---