Lithium carbonaceous materials

This chapter addresses several issues dealing with the mechanism of SEI formation on inert substrates, lithium, carbonaceous materials and tin-based alloys. Attention is currently focused on the correlation between the composition and morphology of the solid-electrolyte interphase forming on the different planes of highly ordered pyrolytic graphite (HOPG) and different types of disordered carbon electrodes in lithium-ion cells. 

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. 

The work presented in this chapter involves the study of high capacity carbonaceous materials as anodes for lithium-ion battery applications. There are hundreds and thousands of carbonaceous materials commercially available. Lithium can be inserted reversibly within most of these carbons. In order to prepare high capacity carbons for hthium-ion batteries, one has to understand the physics and chemistry of this insertion. Good understanding will ultimately lead to carbonaceous materials with higher capacity and better performance. 

To understand the mechanisms for the reaction of lithium with different carbons is the goal of this chapter. However, before we can do this, we need clear structural pictures for carbonaceous materials in each of the three regions. 

There are many ways to eharaeterize the strueture and properties of carbonaceous materials. Among these methods, powder X-ray diffraetion, small angle X-ray scattering, the BET surfaee area measurement, and the CHN test are most useful and are deseribed briefly here. To study lithium insertion in carbonaeeous materials, the eleetroehemieal lithium/earbon eoin eell is the most eonvenient test vehicle. 

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. 

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 electrochemical performance of lithiated carbons depends basically on the electrolyte, the parent carbonaceous material, and the interaction between the two (see also Chapter III, Sec.6). As far as the lithium intercalation process is concerned, interactions with the electrolyte, which limit the suitability of an electrolyte system, will be discussed in Secs. 5.2.2.3,... 

The quality and quantity of sites which are capable of reversible lithium accommodation depend in a complex manner on the crystallinity, the texture, the (mi-cro)structure, and the (micro)morphology of the carbonaceous host material [7, 19, 22, 40-57]. The type of carbon determines the current/potential characteristics of the electrochemical intercalation reaction and also potential side-reactions. Carbonaceous materials suitable for lithium intercalation are commercially available in many types and qualities [19, 43, 58-61], Many exotic carbons have been specially synthesized on a laboratory scale by pyrolysis of various precursors, e.g., carbons with a remarkably high lithium storage capacity (see Secs. 

Because of the variety of available carbons, a classification is inevitable. Most carbonaceous materials which are capable of reversible lithium intercalation can be classified roughly as graphitic and non-graphitic (disordered). 

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-... 

Intercalation compounds of lithium and other species into the layered structure of graphite, synthesized by chemical methods, have been known for a long time. In the mid-1980s, the possibility of a reversible lithium intercalation from apro-tic solutions containing lithium salts into certain carbonaceous materials was discovered ... 

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. 

Due to its high energy density (3,860 mAh/g) and low voltage, lithium is the most attractive metal of the periodic table for battery application. Unfortunately lithium metal, and most of its alloys cannot be used in rechargeable batteries because of their poor cyclability. Therefore, lithium intercalation compounds and reversible alloys are among today s materials of choice for subject application. The most common active materials for the negative electrodes in lithium-ion battery applications are carbonaceous materials. The ability of graphitized carbonaceous materials to... 

Synthetic carbonaceous materials are widely used in these applications. Several types of synthetic materials (e.g. graphitized mesophase carbon microbeads (MCMB), graphitized milled carbon fiber, and even, initially, hard carbons) became the materials of choice at the time of commercialization of first successful lithium-ion batteries in late 1980s. New trends, mainly driven by cost reduction and need for improved performance, currently shift focus towards application of natural graphite. 

The comparison in between natural graphite and other carbonaceous materials has shown that natural graphite having sufficient purity and an optimal set of surface properties can be an outstanding candidate for lithium-ion battery applications. 

Barsukov I.V. Development of low-cost, novel carbonaceous materials for anodes in lithium-ion rechargeable batteries - Superior Graphite Co. Snapshots of CARAT (Cooperative Automotive Research for Advanced Technology) Projects. Publication of OAAT OTTEE RE, U.S. Department of Energy, 9/2001, 26-27. 

CHARACTERIZATION OF ANODES BASED ON VARIOUS CARBONACEOUS MATERIALS FOR APPLICATION IN LITHIUM-ION CELLS... 

Carbonaceous materials with varying degree of graphitic order are the most common commercial anodes in secondary lithium-ion batteries. Among carbon-based materials, natural graphite is the most promising anode... 

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