Über die Elektrolysen von wasserfreiem Phosphoroxychlorid und wasserfreiem Thionylchlorid

Conductance and viscosity of LiAlCl4‐SOCl2 solutions covering a wide range of concentration (10−4–2.0M) have been measured at 25°C and for concentrated solutions these measurements have been made at several temperatures. Parameters characteristic of ion‐ion and ion‐solvent interactions and the energy of activation for conductance and for viscous flow have been obtained. Cyclic voltammograms of LiAlCl4‐SOCl2 solutions at several concentrations have been obtained and the effect of the additives, such as S2Cl2 , SCl2 , SO2 , and SO2Cl2 on the reduction behavior of SOCl2 has been studied as some of these are reduction products of SOCl2 . The implications of these studies on the performance and safety of the lithium‐thionyl chloride battery are discussed.

mentioning

confidence: 80%

Properties of LiAlCl4 ‐ SOCl2 Solutions for Li / SOCl2 Battery

Venkatasetty

Saathoff

1981

“…Electrochemical oxidation of SOC12 was first studied by Spandau et aI. (25). It was reported by these authors that electrolysis of 0.14NI (CfHs)aNHC1/SOC12 solution gave C12 as the oxidation product.…”

Section: Electrolysis Of Soci~/liaici~ Solutionsmentioning

confidence: 99%

Some Chemistry in the Li / SOCl2 Cell

Abraham

Mank

1980

Cyclic voltammetry and constant current electrolysis studies of SOCIs/ LiAlC14 solutions showed that SOeCI~, SOCI+AICI4 -, SC12, AICI~, and C12 are produced as oxidation products. Mechanisms of oxidation reactions are proposed to explain the formation of these products. Forced overdischarge of cathode limited cells produces Li2S which reacts with LiAICl4 present in the cell to form LiAISC12. Materials formed in anode limited cells during forced overdischarge include SOsCI2, SC12, C12, SOCI+AICI4 -, AIC13, and a substance with infrared absorption at 1070 cm -I. "Charging" of Li/SOCI2 cells involves regenerative processes so that only small amounts of products accumulate in the cell. * Electrochemical Society Active Member.

“…The electrochemical reduction of solvents, in solutions of triethylammonium chloride in phosphorous oxychloride and thionyl chloride, at platinum electrodes was first reported by Spandau, Beyer, and Preugschat (5). The cathodic product in the case of POC13 was found to have the stoichiometric formula PO and is believed to be polymeric.…”

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confidence: 92%

“…The voltammetric reduction of the solvents in solutions of LiBC14 in POC13 and LiA1C14 in SOC12 at platinum, pyrolytic graphite and porous carbon electrodes was confirmed (6) in this laboratory using the techniques of cyclic and rotating ring-disk voltammetry. Assuming the cathodic reaction products to be the same as postulated by Spandau et al (5), the net cell reaction in cell I may be given by the following equation 3Li + POCI~ ~ PO -t-3LiC1 [1] Since SO2 is known (7) to undergo further reduction in anhydrous nonaqueous solvents to dithionate ($204--) and C12 to chloride (C1-) (6) ions, the net cell reaction in cell II may be given by the following equation 8Li + 4SOC12 ~ Li2S204 + 6LiC1 -t-$2C12 [2] Assuming the net cell reactions given by Eq. [1] and [2] to be correct for cells I and II, respectively, the approximate free energy changes for reactions [1] and [2] are calculated from the open-circuit voltages to be, respectively, --214 kcal/mole of POC13 and --168 kcal/ mole of SOC12.…”

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confidence: 99%

Lithium Inorganic Electrolyte Cells Utilizing Solvent Reduction

Behl

Christopulos

Ramirez

et al. 1973

This paper describes a study of room temperature lithium cells employing solutions of LiBCl4 in POCl3 and LiAlCl4 in SOCl2 as electrolytes and polytetrafluoroethylene (Teflon)‐bonded carbon black electrodes as cathodes. A novel feature of these cells is that during discharge the solvents, i.e., POCl3 and SOCl2 , are electrochemically reduced and behave as soluble cathodes. Sealed prototype cells were fabricated using a polyethylene‐polyester laminated bag container. Based on total cell weight, a prototype cell yielded an experimental energy density of 244 W‐hr/lb for a 57‐hr discharge rate (20 mA constant current; 1 mA/cm2 current density). The performance of these cells is also compared with the performance of prototype lithium‐organic electrolyte‐graphite monofluoride and lithium‐inorganic electrolyte‐tetracarbon monofluoride cells.