Lithium thermodynamic properties

A series of experiments have been undertaken to evaluate the relevant thermodynamic properties of a number of binary lithium alloy systems. The early work was directed towards determination of their behavior at about 400 °C because of interest in their potential use as components in molten salt batteries operating in that general temperature range. Data for a number of binary lithium alloy systems at about 400 °C are presented in Table 1. These were mostly obtained by the use of an experimental arrangement employing the LiCl-KCl eutectic molten salt as a lithiumconducting electrolyte. 

Anani A., Crouch-Baker S., Huggins RA. Kinetic and Thermodynamic Properties of Several Binary Lithium Alloy Negative Electrode Materials at Ambient Temperature. J. Electrochem. Soc. 1987 134 3098-101. 

Lithium electrodes, 3 408 standard potential, 3 413t Lithium fluoride, 15 138-139 Lithium fluoroborate, 4 153 manufacture, 4 155 physical properties of, 4 152t thermodynamic properties of, 4 154t uses of, 4 157... 

The purpose of this study is to examine the structural features of acetonitrile-water mixtures over the whole composition range using the heats of solution and dilution of lithium perchlorate as a probe. The effect of water on thermodynamic properties such as heats of solution is also of interest. 

The work with which we are chiefly concerned here is an extension of these investigations of the effects of water on the thermodynamic properties of electrolytes in DPA solvents. The electrolytes considered are acids (HA), whose importance as a class of electrolytes derives from their involvement in many chemical reactions, either as reactants or as catalysts. In conjunction with these investigations, a parallel study was carried out water was replaced by diethyl ether (Et20) to determine the extent to which the hydrogen bond donor properties of the water molecule affect the interactions between HA, H20, and the solvent. For comparison, some additional experiments were included that used as electrolytes a lithium salt and a chloride salt and H2S instead of H20. 

Finally, a brief overview was presented of important experimental approaches, including GITT, EMF-temperature measurement, EIS and PCT, for investigating lithium intercalation/deintercalation. In this way, it is possible to determine - on an experimental basis - thermodynamic properties such as electrode potential, chemical potential, enthalpy and entropy, as well as kinetic parameters such as the diffusion coefficients of lithium ion in the solid electrode. The PCT technique, when aided by computational methods, represents the most powerful tool for determining the kinetics of lithium intercalation/deintercalation when lithium transport cannot be simply explained based on a conventional, diffusion-controlled model. 

SMI/MOS] Smith, J. F., Moser, Z., Thermodynamic properties of binary lithium systems - a review, J. Nucl. Mater., 59, (1976), 158-174. Cited on page 412. 

CHE/MOR] Chekoev, N. G., Morachevskii, A. G., Thermodynamic properties of lithium-selenium system melts, Zh. Prikl. Khim. (S.-Peterburg), 51, (1978), 2348-2350, in Russian. Cited on page 412. 

The standard free energy of formation (kcalmoF ) of liquid lithium hydride is given by (13.47 x lO T -16.55). The thermodynamic properties of the Li-LiH system have been determined by a mass spectrometric Knudsen effusion method in the plateau region from 973 to 1146 K. The enthalpy, AHitjs, of the reaction... 

Because in the west of China some salt lake brines contain abundant boron and lithium, in which solute-solvent and solute-solute interactions are complex, studies on the ihermochemical properties for the systems related with the brines are essential to understand the effects of temperature on excess free energies and solubility, and to build a thermodynamic model that can be applied for prediction of the properties. Yin et al. [43] measured the enthalpies of dilution for aqueous Li2B407 solutions from 0.0212 to 2.1530 mol/kg at 298.15 K. The relative apparent molar enthalpies and relative partial molar enthalpies of the solvent and solute were also calculated, and the thermodynamic properties of the complex aqueous solutions were represented by a modified Pitzer ion-interaction model. 

The thermodynamic properties of the lithium halides have been reported in detail. " In all cases, the E values of the cell... 

The thermodynamic properties of aluminum antimonide have been previously studied by the electromotive force (emf) method using aluminum chloride as the electroljrte in fused lithium and potassium chlorides [4], The calculated value [4] of the standard entropy of solid aluminum antimonide S 98 = 6.0 0.8 eu/g-atom and that obtained by Piesbergen [5] from measurements of low-temperature specific heat, = 7.68 0.05 eu/g-atom do not agree even within the... 

Sharma RA, Seefurth RN (1976) Thermodynamic properties of the lithium-silicon system. J Electrochem Soc 123 1763-1768... 

Weppner W. and Huggins R.A. thermodynamic properties of the intermetallic systems Lithium-Antimony and Lithium- Bismuth, (1978) J. Electrochem. Soc., 125, 7-14. 

Rabinovich s collection of data includes some thermodynamic properties of carbon dioxide, water, lithium, mercury, ethylene, butene, halogenated monosilanes and methanes, liquid ammonia, and hydrogen peroxide, and the densities of liquid alkali metals. 

Americium metal has been prepared by the following methods (1) reduction of AmF3 with barium (or lithium) metal (2) reduction of Am02 with lanthanum metal (3) bomb reduction of AmF4 with calcium metal (4) thermal decomposition of Pts Am. Lanthanum reduction of Am02 in tantalum equipment and subsequent distillation of the americium metal from the reaction mixture yields americium of very high (>99.9%) purity. There is about 10 -fold difference in americium-lanthanum volatility. Extensive application of this technique by the Euratom group has led to important new measurements of the physical properties and thermodynamic properties of americium metal [81,342], Rocky Flats workers have reported similar success with vacuum distillation [333]. 

The lithium-tin binary system is somewhat more complicated, as there are six intermediate phases, as shown in the phase diagram in Figure 14.5. A thorough study of the thermodynamic properties of this system was undertaken [27]. The composition dependence of the potential at 415 °C is shown in Figure 14.6. 

A. N. Campbell and 0. N. Bhatnagar, Can. J. Chem., 50, 1627 (1972). Some thermodynamic properties of lithium chlorate in water and water-dioxane mixtures. Heats of solution and dilution. 

Ferloni P, Kenesey C, Westrum EF Jr (1994) Thermodynamics of alkali alkanoates X. Heat capacities and thermodynamic properties of lithium methanoate and lithium ethanoate at temperatures from 5 K to 580 K. J Chem Thermodyn 26 1349-1363... 

Various Chemical and Thermodynamic Properties of Lithium A. Lithium Metal (CAS No. 7439-93-2)... 

This review has discussed only continuum-scale models. Other types of models are also used in the study of lithium batteries. Empirical models are used to predict battery life by extrapolating experimental results. Statistical mechanical mcxiels help in understanding transport on the molecular level and also in understanding thermodynamic properties of insertion compounds. For example,... 

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