Deintercalation process

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. 

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 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. 

The temperature dependence of the reaction was studied, and the activation energy of the reaction was calculated to be approximately 100 kj mol The exponent n was found to lie in the range 1-2, which is consistent with a 2D diffusion controlled reaction mechanism with deceleratory nucleation. The rate of reaction increases markedly with the amount of water added to the LDH with very small amounts of water added, the deintercalation process does not go to completion. This effect is a result of the LiCl being leached into solution. An equilibrium exists between the LDH and gibbsite/LiCl in solution. The greater [LiCl], the further to the LDH side this lies. 

Experiments were performed with various LiAl-X LDHs, with X = Br, NO3 and ISO4. As with the intercalation process, the nature of the anion exerts a powerful influence on the reaction. In the case of sulfate, the deintercalation reaction does not go to completion - only 40% of the available lithium sulfate was released. The deintercalation reaction initially proceeds very quickly, but the process is then halted. The rate of deintercalation is NOs" > Cl > Br . This series does not correspond with data on the anion selectivity for intercalation into Al(OH)3, which is S04 > Cl" > Br" > NO3". Neither is there a correlation of the release data with the heats of hydration of the anions. The series observed arises because the intercalation and deintercalation processes are a balance of a number of factors, including interactions between the guest ions and the host matrix. 

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.

This work consist of a two adding one another experimental parts, discussion and conclusions. In the first experimental part, we report about our investigations of hydrogen intercalation-deintercalation processes in layered InSe and GaSe crystals and powders. In the second one, the influence of intercalated hydrogen on optical properties of these crystals is reported. 

Figure 2. a - 2D sketch illustrate processes of intercalation and deintercalation of hydrogen in layered crystals like InSe and GaSe. 

Zhirko Yu.I., Kovalyuk Z.D., Pyrlja M.M., Boledzyuk V.B. (2003) Optical Investigation of Hydrogen Intercalation-Deintercalation Processes in Layered Semiconductor y-InSe Crystals. Proceeding of VIII Int. Confer. Hydrogen Material Science Chemistry of Carbon Nanomaterials 1157. 

As discussed in the next section, lithiated carbon electrodes are covered with surface films that influence and, in some cases, determine their electrochemical behavior (in terms of stability and reversibility). They are formed during the first intercalation process of the pristine materials, and their formation involves an irreversible consumption of charge that depends on the surface area of the carbons. This irreversible loss of capacity during the first intercalation/deintercalation cycle is common to all carbonaceous materials. However, several hard, disordered carbons exhibit additional irreversibility during the first cycle, in addition to that related to surface reactions with solution species and film formation. This additional irreversibility relates to consumption of lithium at sites of the disordered carbon, from which it cannot be electrochemically removed [346-351],... 

As mentioned earlier, intercalation of alkali metals in host solids in readily accomplished electrochemi-cally. It is easy to see how both intercalation (reduction of the host) and deintercalation (oxidation of the host) are processes suited for this method. Thus, lithium intercalation is carried out using a lithium anode and a lithium salt in a non-aqueous solvent... 

FIGURE 26.8 Slow-scan cychc voltammograms obtained on synthetic graphite indicate that all the intercalation/deintercalation processes proceed within a potential range of 0.25 V vs. Li/Lri. 

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