Electrochemical lithium intercalation

Funabiki A, Inaba M, Ogumi Z, Yuasa S, Otsuji J, Tasaka A. Impedance study on the electrochemical lithium intercalation into natural graphite Powder. J Electrochem Soc 1998 145 172-178. 

Leroux F, Koene BE, Lazar LF. Electrochemical lithium intercalation into a polyaniline/V205 nanocomposite. J Electrochem Soc 1996 143 L181-L183. 

Empty perovskite lattices can also form oxygen deficient phases by a process known as Crystallographic Shear, which introduces edge-sharing octahedra in addition to comer sharing. Examples include the reduced molybdenum oxides M08O23, M09O26, and VeOis. The latter is a metallic phase with substantial reversible capacity for electrochemical lithium intercalation between 2.8 and 2.2 V with respect to lithium metal. 

Figure 10. (a) Nyquist plots obtained with a Li. sNi02 electrode at various electrode potentials, (b) Equivalent circuit used for analysis of the electrochemical lithium intercalation reaction into Li NiOj. CPE, = C/Qco) (/ = contact or adsorption), where C, is... 

In 1975, Whittingham was first to report the reversible electrochemical lithium intercalation into vanadium pentoxide [11]. V2O5 electrodes are expected to undergo lithium ion insertion accompanied by several structural modifications, occurring in several consecutive stages [21, 22]... 

Electrochemical Lithium Intercalation Reaction of Anodic Vanadium Oxide Film. J. Alloys Compounds 217, 52—58. 

Cai K.F., Muller E., Drasar C., Mrotzek A. Preparation and thermoelectric properties of Al-doped ZnO ceramics. Mater. Sci. Eng. B 2003 104 45 8 Candy J.P., Fouilloux P., Keddam M., Takenouti H. The characterization of porous-electrodes by impedance measurements. Electrochimica Acta 1981 26 1029-1034 Choi Y.M., Pyun S.I., Moon S.I., Hyung Y.E. A study of the electrochemical lithium intercalation behaviour of porous LiNi02 electrodes prepared by solid-state reaction and sol-gel methods. J. Power Sources 1998 72 83-90... 

It has been known for a long time that lithium ion can be intercalated within graphite to form Li-GIC since the discovery by Herold [13] in 1955. (The first success in electrochemical lithium intercalation was reported in a patent of Sanyo in 1981 [14].) The phase diagram of Li-GIC, which was obtained by an... 

Ambach D, Gamolsky K, Markovsky B, Salitra G, Gofer Y, Heider U, Oesten R, Schmidt M (2000) The study of surface phenomena related to electrochemical lithium intercalation into LUMOy host materials (M = Ni, Mn). J Electrochem Soc 147 1322-1331... 

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. 

Lavela P, Comad M, Mrotzek A, Harbrecht B, Tirado JL (1999) Electrochemical lithium and sodium intercalation into the tantalum-rich layered chalcogenides Ta2Se and Ta2Te3. J AUoy Compd 282 93-100... 

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. 

Figure 17. The basal plane and prismatic surfaces of graphite have different functions with respect to lithium intercalation and de-intercalation (= charge, discharge, self-discharge, etc.). As a consequence, only the electrolyte decomposition product layers at the prismatic surfaces have SEIfunction. Any processes related with electrolyte decomposition product layers at the basal plane surfaces (= non-SEI layers) therefore can not be directly related to electrochemical data such as charge, discharge, self-discharge, etc. The situation is even more complex as the SEI composition and morphology at the basal and prismatic surface...

Billaud D., Henry F.X. and Willmann P. Electrochemical Synthesis of Binary Graphite-Lithium Intercalation Compounds. Mat. Res. Bull., 28, 477-483 (1993). 

Composite electrodes made of two carbon components were evaluated experimentally as anodes for Li-ion batteries. The electrochemical activity of these electrodes in the reaction of reversible lithium intercalation ffom/to a solution of LiPF6 in ethyl carbonate and diethyl carbonate was studied. Compositions of the electrode material promising for the usage in Li-ion batteries were found. 

The source carbon materials show a significant electrochemical activity for lithium intercalation though the reversible capacity is relatively low and tends to reduce with cycling. For the thermally expanded graphite... 

Electrochemical Properties of Modified Carbons in the Reaction of Lithium Intercalation... 

Perhaps the most well known of the lithium intercalation compounds is Li jTiSj. Both Li (for x < 1) and Ti are octahedrally coordinated by S (Fig. 7.1) in the ABC notation, the structure is AbC(b)AbC, where the letter in parentheses denote lithium atoms. This structure is also called the IT form, because of its trigonal (T) symmetry and the single layer per unit cell. The electrochemical behaviour of Li in TiSj is described below in connection with staging. 

Vanadium diselenide also showed the feasibility of intercalating a second lithium into the lattice. The LiVSe2/Li2VSe2 system must be two phase, as the lithium in LiVSe2 is in octahedral coordination whereas in Li2VSe2 the lithium must move to tetrahedral coordination and both sites cannot be occupied at the same time. This two-lithium intercalation can be accomplished either electrochemically or chemically, for example, by using butyllithium. Other dilithium layered materials such as Li2Ni02 have also been formed both electrochemically and chemically... 

Murphy et al. made an extensive study of a number of vanadium oxides and discovered the excellent electrochemical behavior of the partially reduced vanadium oxide, VeOis, which reacts with up to 1 LiA/. They also recognized that the method of preparation, which determines the V 0 ratio, critically controls the capacity for reaction with lithium. The structure consists of alternating double and single sheets of vanadium oxide sheets made up of distorted VOe octahedra. A variety of sites are available for lithium intercalation, which if filled sequentially would lead to the various steps seen in the discharge curve. The lattice first expands along the c-axis and then along the b-axis. Thomas et ai 87 91 an in-depth study of the complex... 

Figure 11. (a) Initial IV2 cycles of a Li/petroleum coke cell. The cell was cycled at a rate of 12.5 h for Ax = 0.5 in Li sG6. (b) Initial IV2 cycles of a Li/graphite cell. The cell was cycled at a rate of 40 h for Ax= 0.5 in Li sG6. F denotes the irreversible capacity associated with SEI formation, E the irreversible capacity due to exfoliation, and I the reversible capacity due to lithium intercalation into carbon. 1.0 M LiAsEe in EC/PC was used as electrolyte. (Reproduced with permission from ref 36 (Eigure 2). Copyright 1990 The Electrochemical Society.)... 

Figure 16. Voltage profiles for the first two lithium intercalation/deintercalation cycles realized on graphite anode in t-BC/EMC and c-BC/EMC solutions of 1.0 M LiPEe. (Reproduced with permission from ref 255 (Eigure 7). Copyright 2000 The Electrochemical Society.)...

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