Intercalation carbonaceous anodes

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. 

The Li-Ion system was developed to eliminate problems of lithium metal deposition. On charge, lithium metal electrodes deposit moss-like or dendrite-like metallic lithium on the surface of the metal anode. Once such metallic lithium is deposited, the battery is vulnerable to internal shorting, which may cause dangerous thermal run away. The use of carbonaceous material as the anode active material can completely prevent such dangerous phenomenon. Carbon materials can intercalate lithium into their structure (up to LiCe). The intercalation reaction is very reversible and the intercalated carbons have a potential about 50mV from the lithium metal potential. As a result, no lithium metal is found in the Li-Ion cell. The electrochemical reactions at the surface insert the lithium atoms formed at the electrode surface directly into the carbon anode matrix (Li insertion). There is no lithium metal, only lithium ions in the cell (this is the reason why Li-Ion batteries are named). Therefore, carbonaceous material is the key material for Li-Ion batteries. Carbonaceous anode materials are the key to their ever-increasing capacity. No other proposed anode material has proven to perform as well. The carbon materials have demonstrated lower initial irreversible capacities, higher cycle-ability and faster mobility of Li in the solid phase. 

Hence, a dilemma was encountered between energy density and stability for these various forms of carbonaceous materials that is, as the carbonaceous anode is more graphitic in structure, the degree of lithium ion intercalation may be closer to the ideal x = 1.0), and its potential profile may be closer to that of Li+/Li and remain relatively flat (therefore... 

On the basis of the above observation, Dahn and co-workers proposed a thermal reaction scheme for the coupling of carbonaceous anodes and electrolytes. The initial peak, which was almost identical for all of the anode samples and independent of lithiation degrees, should arise from the decomposition of the SEI because the amount of SEI chemicals was only proportional to the surface area. This could have been due to the transformation of the metastable lithium alkyl carbonate into the stable Li2C03. After the depletion of the SEI, a second process between 150 and 190 °C was caused by the reduction of electrolyte components by the lithiated carbon to form a new SEI, and the autocatalyzed reaction proceeded until all of the intercalated lithium was consumed or the thickness of this new SEI was sufficient to suppress further reductions. The corresponding decrease in SHR created the dip in the least lithiated sample in Eigure 35. Above 200 °C (beyond the ARC test range as shown in Eigure 35), electrolyte decomposition occurred, which was also an exothermic process. 

The feasibility of the gel electrolytes for lithium-ion batteries development has been tested by first examining their compatibility with appropriate electrode materials, i.e., the carbonaceous anode and the lithium metal oxide cathode. This has been carried out by examining the characteristics of the lithium intercalation-deintercalation processes in the electrode materials using cells based on the given polymer as the electrolyte and lithium metal as the counter electrode. 

In this case a potassium-graphite (KCg) electrode has been used as the carbonaceous anode material. Upon anodic polarisation this electrode irreversibly deintercalates potassimn resulting in a graphite-like compound, which on subsequent cycles performs with fast kinetics of its lithium intercalation-deintercalation process [89, 90]. Accordingly, the first charging process of the battery may be written as shown in Equation 7.7 at the anode. 

In the meantime, it was demonstrated that lithium can be reversibly inserted into graphite at room temperature in an organic electrolyte in 1983. Lithium-ion battery was first commercialized with this carbon-based anode in 1991. Graphite bas a capacity of 372 mAh/g, corresponding to the intercalation of one lithium atom per six carbon atoms. Though carbon bas ratber lower capacity than lithium metal and lithium alloy anodes, volume change was small and represented longer cycle performance. After this commercialization, many researchers and companies have put their effort on new carbonaceous anodes. 

A wide variety of carbonaceous materials can intercalate or insert lithium reversibly and thus may be candidates for anodes for lithium ion batteries. In recent years, many types of carbons have been tested as alternative anodes for rechargeable lithium batteries, part of which have found use as anodes in practical, commercial lithium ion batteries. The most straightforward way of classifying these electrodes is according to the type of the carbon, which determines their capacity and basic electrochemical behavior. The major types of carbons tested in recent years as anode materials for Li ion batteries are listed below ... 

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