Lithium-Inorganic Electrolyte Batteries

Holleck, G. L.; Turchan, M.; Cogley, David R.

doi:10.21236/ada005057

Cited by 8 publications

(20 citation statements)

References 2 publications

(6 reference statements)

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“…In x = ----+ (0.057 ± 0.432) (5) The heat of fusion calculated from eq 5 is 2758 cal/gram formula weight, in good agreement with the accepted heat of fusion of cyclooctasulfur, 2696 cal/gram formula weight (again suggesting that the sulfur dissolves as the cyclic octamer).…”

Section: Resultssupporting

confidence: 73%

“…Sulfur and sulfur dioxide are both produced during the normal discharge of the lithiumjthionyl chloride primary battery, and both are soluble in the thionyl chloride electrolyte (1)(2)(3)(4). However, once the solubility of the sulfur has been exceeded, it precipitates within the cathode and the separator (contributing to decreased cell capacity and efficiency) (1,5). Likewise, once the solubility of the sulfur dioxide has been exceeded, pressures beyond 1 atm will build up within the cell (3,6).…”

Section: Introductionmentioning

confidence: 99%

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Solubilities of sulfur and sulfur dioxide in thionyl chloride with and without 1.8 M lithium tetrachloroaluminate

Klinedinst¹,

McLaughlin²

1979

J. Chem. Eng. Data

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The solubilities of S and S02 in SOCI2 containing 1,8 M LiAICI4 have been determined as a function of temperature. Sulfur solubility data have been obtained for temperatures between 0 and 55 °C, while the data for S02 solutions cover the range of temperatures between 0 and 60 °C. Over the temperature range considered here, the sulfur solubility increases with temperature In an approximately linear fashion. In contrast, the S02 solubility decreases with increasing temperature, and the relationship between molar solubility and temperature is an approximately parabolic one. Additionally, the effects of the presence of water or the products of the reaction between water and SOCI2 upon the dissolution of sulfur in SOCI2 have been examined. It has been found that neither hydrolysis product has a very significant effect upon the sulfur solubility, whereas H20 Itself readily causes sulfur to precipitate from solution.

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Section: Resultssupporting

confidence: 73%

Section: Introductionmentioning

confidence: 99%

Solubilities of sulfur and sulfur dioxide in thionyl chloride with and without 1.8 M lithium tetrachloroaluminate

Klinedinst¹,

McLaughlin²

1979

J. Chem. Eng. Data

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“…(Fig. 7) on Ni working electrodes in the NbC1JLi2S combination electrolyte are very similar to those in LiA1C14 electrolyte (17,18). Since the potential at which the reactions occur is the same in both electrolytes, the use of the NbC1JLLS should not affect the operating voltage in battery cells.…”

Section: Resultsmentioning

confidence: 52%

Reduction of Voltage Delay in the Li / SOCl2 System via Suitable Choice of Electrolyte Salts

Fleischer¹,

Manske²,

Ekern³

1984

J. Electrochem. Soc.

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New electrolyte salts based on the reaction between NbCl5 and either Li2S or Li2O in SOCl2 substantially reduce voltage delay in laboratory half‐cells. The maximum effect was obtained with the NbCl5/Li2S combination. The conductivity of both electrolytes is 13.2×10−3 mho cm−1 at 26°C. Observations with scanning electron microscopy (SEM) show that the anode film formed in the new electrolyte has a different morphology and appears less dense than the film formed in control LiAlCl4 electrolyte. The anodic rate capability of Li is slightly greater, over a range of over‐potentials, in the normalNbCl/Li2S electrolyte than in LiAlCl4 . Atomic absorption, infrared, and x‐ray photoelectron spectroscopy and electrochemical analysis suggest that the salt formed by reacting NbCl5 with Li2S in SOCl2 is either Li2Nb2Cl10S or Li2Nb2Cl12 . The mechanism for reducing voltage delay and affecting anode film morphology is thought to be associated with the nature of the salt's anion, or possibly the SO2 produced when Li2S is combined with the NbCl5 in SOCl2 .

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“…Solutions saturated with sulfur and sulfur dioxide, with and without LiAICI4, with and without fresh or used cathode material, failed to produce hysteresis similar to that seen for the used electrolyte, even when the fresh mixtures were recycled to 100~ Reactions [10], [11], or [12] could therefore not have occurred under these conditions. Figure 14 shows the result when used electrolyte was so cycled.…”

Section: Vt : E ~-T (Oe/ot) : --(~H/nf) : 334v [8]mentioning

confidence: 94%

Discharge Reaction Mechanisms in Li / SOCl2 Cells

Schlaikjer¹,

Goebel²,

Marinčić³

1979

J. Electrochem. Soc.

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The processes taking place during the discharge of Li/SOC12/C cells were studied. Test vehicles included wound D, bobbin configuration 2D cells, and 2000 A-hr prismatic cells. Dried cathodes taken from 2D cells, discharged at 150 mA were analyzed quantitatively for lithium-sulfur oxyaeid salts. Little or no such salt was found for cells discharged at ambient temperature. Measurements of the open-circuit voltage of this system as a function of temperature showed essentially linear dependence with positive slope between ~-72 ~ and --20~ but the voltage fell more steeply as the temperature approached --60~Appearance of a nonvolatile reducing species occurred in the cathodes of cells discharged at --20~ which were not present in cathodes from cells discharged at higher temperature. Controlled potential electrolysis of supporting electrolytes containing limited amounts of SOCI.~ were carried out between 0 ~ and 25~ The electrical equivalent of thionyl chloride was found to be between 1.5 and 2.0 F/mole. The 200,0 A-hr cells were used to measure dissolved SO2 and SO2 escaping at atmospheric pressure and ambient temperature from anode-limited and cathode-limited cells. The amount of SO2 produced was found to be only a fraction of that predicted by 4Li ~-2SOCls -+ S § SO2 + 4LiC1 until near the end of discharge. The total amount of SOs produced by the end of discharge was not more than predicted by this reaction. Vented, anode-limited cells did not release SO2 while cathode-limited cells did. Temperature cycling of electrolyte taken from cells immediately after discharge was carried out in a sealed vessel. Pressure hysteresis occurred, which could not be duplicated with simulated used electrolyte made with S, SOs, SOC12, LiA1C14, and cathode material. At --20~ and below, the discharge reaction 8Li + 3SOCls-~ 2S ~-Li2SO8 ~-6LiC1 may be significant, while at temperatures higher than this, the reaction 2nLi + nSOC12-~ 2nLiC1 + (SO), may predominate, where the (SO)n remains in solution. Slow decomposition according to (SO)h-> (n/2)S + (n/2)SOz may subsequently take place.

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Lithium-Inorganic Electrolyte Batteries

Cited by 8 publications

References 2 publications

Solubilities of sulfur and sulfur dioxide in thionyl chloride with and without 1.8 M lithium tetrachloroaluminate

Solubilities of sulfur and sulfur dioxide in thionyl chloride with and without 1.8 M lithium tetrachloroaluminate

Reduction of Voltage Delay in the Li / SOCl2 System via Suitable Choice of Electrolyte Salts

Discharge Reaction Mechanisms in Li / SOCl2 Cells

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