Carbonaceous electrode

Perhaps the first practical application of carbonaceous materials in batteries was demonstrated in 1868 by Georges Le-clanche in cells that bear his name [20]. Coarsely ground MnO, was mixed with an equal volume of retort carbon to form the positive electrode. Carbonaceous powdered materials such as acetylene black and graphite are commonly used to enhance the conductivity of electrodes in alkaline batteries. The particle morphology plays a significant role, particularly when carbon blacks are used in batteries as an electrode additive to enhance the electronic conductivity. One of the most common carbon blacks which is used as an additive to enhance the electronic conductivity of electrodes that contain metal oxides is acetylene black. A detailed discussion on the desirable properties of acetylene black in Leclanche cells is provided by Bregazzi [21], A suitable carbon for this application should have characteristics that include (i) low resistivity in the presence of the electrolyte and active electrode material, (ii) absorption and retention of a significant... 

Carbon Electrodes. Carbon electrodes are rigid carbonaceous shapes deployed in electric furnaces. They are the final link in the chain of conductors from the energy source to the reaction zone of an electrically heated vessel. The gap bridged by the electrode is that between the contact plates that transmit current to the electrode and the discharge area at the arc end of the electrode. 

Two types of carbon electrodes are in widespread use. Prebaked carbon electrodes (Fig. 5) are those made from a mixture of carbonaceous particles and a coal-tar pitch binder. The electrode is formed by extmsion or mol ding from a heated plasticlike mix and subsequently baked. Final bake temperature is sufficient to carbonize the binder, ie, about 850°C. At this temperature the binder is set, all volatiles have left, and a significant portion of the product shrinkage has occurred. 

Self-baked carbon electrodes are those whose shapes are formed in situ (33). The carbonaceous mixture is placed into a hoUow tube-shaped metal casing. The upper end receives the unbaked mixture as a soHd block, small particles, or warm plastic paste. The casing contains inwardly-projecting longitudinal perforated fins that become surrounded by baked carbon as the casing is incrementally moved downward and through the contact plates. Casing and carbon are consumed in this furnace. 

One criterion for the anode material is that the chemical potential of lithium in the anode host should be close to that of lithium metal. Carbonaceous materials are therefore good candidates for replacing metallic lithium because of their low cost, low potential versus lithium, and wonderful cycling performance. Practical cells with LiCoOj and carbon electrodes are now commercially available. Finding the best carbon for the anode material in the lithium-ion battery remains an active research topic. 

For convenience and simplicity, the electrochemical study of electrode materials is normally made in lithium/(eleetrode material) eells. For earbonaeeous materials, a hthium/carbon eell is made to study electroehemical properties, sueh as eapaeity, voltage, eyeling life, etc.. Lithium/carbon coin cells use metallie lithium foil as the anode and a partieular carbonaceous material as the... 

Lithium/carbon cells are typically made as coin cells. The lithium/carbon coin cell consists of several parts, including electrodes, separator, electrolyte and cell hardware. To construct a coin cell, we first must prepare each part separately. Successful cells will lead to meaningful results. The lithium/carbon coin cells used metallic lithium foil as the anode and a carbonaceous material as the cathode. The metallic lithium foil, with a thickness of 125 pm, was provided by Moli Energy (1990) Ltd.. Idie lithium foil is stored in a glove-box under an argon atmosphere to avoid oxidation. 

The current for charge and discharge is selected based on the active mass of the carbonaceous electrode. A 50-h-rate current applied to the cell corresponds to a change Ax = 1 in Li Q in 50 hours (for a typical cell with 14-mg active carbon mass, the current is 104 pA). The parameter x is the concentration of lithium in the carbonaceous electrode. 

Multi-walled CNTs (MWCNTs) are produced by arc discharge between graphite electrodes but other carbonaceous materials are always formed simultaneously. The main by-product, nanoparticles, can be removed utilizing the difference in oxidation reaction rates between CNTs and nanoparticles [9]. Then, it was reported that CNTs can be aligned by dispersion in a polymer resin matrix [10]. However, the parameters of CNTs are uncontrollable, such as the diameter, length, chirality and so on, at present. Furthermore, although the CNTs are observed like cylinders by transmission electron microscopy (TEM), some reports have pointed out the possibility of non-cylindrical structures and the existence of defects [11-14]. 

Carbonaceous materials serve several functions in electrodes and other cell components for aqueous-electrolyte batteries, and these are summarized in Table 1. 

Of practical importance is the contribution that is made by carbonaceous materials as an additive to enhance the electronic conductivity of the positive and negative electrodes. In other electrode applications, carbon serves as the electrocatalyst for electrochemical reactions and/or the substrate on which an electrocatalyst is located. In... 

There are some other matters that should be considered when comparing metallic lithium alloys with the lithium-carbons. The specific volume of some of the metallic alloys can be considerably lower than that of the carbonaceous materials. As will be seen later, it is possible by selection among the metallic materials to find good kinetics and electrode potentials that are sufficiently far from that of pure lithium for there to be a much lower possibility of the potentially dangerous forma-... 

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. 

It is well known today that the SEI on both lithium and carbonaceous electrodes consists of many different materials including LiF, Li2C03, LiC02R, Li20, lithium alkoxides, nonconductive polymers, and more. These materials form simultaneously and precipitate on the electrode as a mosaic of microphases [5, 6], These phases may, under certain conditions, form separate layers, but in general it is more appropriate to treat them as het-eropolymicrophases. We believe that Fig. 13(a) is the most accurate representation of the SEI. 

Yazami et al. [128, 129] studied the mechanism of electrolyte reduction on the carbon electrode in polymer electrolytes. Carbonaceous materials, such as cokes from coal pitch and spherical mesophase and synthetic and natural graphites, were used. The change in with composi-... 

Kinetic stability of lithium and the lithiated carbons results from film formation which yields protective layers on lithium or on the surfaces of carbonaceous materials, able to conduct lithium ions and to prevent the electrolyte from continuously being reduced film formation at the Li/PC interphase by the reductive decomposition of PC or EC/DMC yielding alkyl-carbonates passivates lithium, in contrast to the situation with DEC where lithium is dissolved to form lithium ethylcarbonate [149]. EMC is superior to DMC as a single solvent, due to better surface film properties at the carbon electrode [151]. However, the quality of films can be increased further by using the mixed solvent EMC/EC, in contrast to the recently proposed solvent methyl propyl carbonate (MPC) which may be used as a single sol-... 

Real reasons due to (a) the occurance of very fast (and therefore in most cases diffusion controlled) catalytic reactions on the electrode surface, (b) Formation of non-conducting carbonaceous or oxidic layers on the catalyst electrode surface. 

There is a third real reason for deviations from Eq. (5.18) in the case that a non-conductive insulating product layer is built via a catalytic reaction on the catalyst electrode surface (e.g. an insulating carbonaceous or oxidic layer). This is manifest by the fact that C2H4 oxidation under fuel-rich conditions has been found to cause deviations from Eq. (5.18) while H2 oxidation does not. A non-conducting layer can store electric charge and thus the basic Eq. 5.29 (which is equivalent to Eq. (5.18)) breaks down. 

Carbon refers to all kinds of carbonaceous, graphitic or similar electrode materials including glassy carbon. 

Great promise exists in the use of graphitic carbons in the electrochemical synthesis of hydrogen peroxide [reaction (15.21)] and in the electrochemical reduction of carbon dioxide to various organic products. Considering the diversity in structures and surface forms of carbonaceous materials, it is difficult to formulate generalizations as to the influence of their chemical and electron structure on the kinetics and mechanism of electrochemical reactions occurring at carbon electrodes. 

Allen GC, Tucker PM, Capon A, Parsons R. 1974. X-ray photoelectron-spectroscopy of adsorbed oxygen and carbonaceous species on platinum-electrodes. J Electroanal Chem 50 335-343. 

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