Sources of Pressure in Lithium Thionyl Chloride Batteries

McDonald, Robert

doi:10.1149/1.2123566

Cited by 5 publications

(2 citation statements)

References 10 publications

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“…The presence of water as a safety factor in SOC12 cells has received little attention. Studies have primarily addressed the effect of water on voltage delay or hydrolysis reactions that produce HC1 or H2 gas (7)(8)(9). Water has been shown to increase cell capacity of reverse polarity SOCI~ ceils following storage at room temperature (10).…”

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Physical and Chemical Characteristics of Hermetically Sealed High Rate Li / SOCl2 C‐Cells

Abraham

Pitts

Kilroy

1985

J. Electrochem. Soc.

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Pressure‐temperature‐voltage relationships in hermetically sealed high rate normalLi/SOCl2 cells have been studied using specially instrumented C‐size cells. The cells generated considerably lower pressures than those expected on the basis of established discharge reactions. This is believed to be due to the SO2 generated being complexed by LiAlCl4 and/or absorbed by the carbon cathode. Li‐limited cells produced lower internal temperatures and pressures towards the end of discharge and during voltage reversal than cathode‐limited cells. In high rate discharge involving >10 mA/cm2, Co‐TAA‐catalyzed cathode cells exhibited higher capacities and lower IR heating than uncatalyzed cells. Li‐limited Co‐TAA catalyzed cathode cells appear to be a desirable design for high rate applications.

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Physical and Chemical Characteristics of Hermetically Sealed High Rate Li / SOCl2 C‐Cells

Abraham

Pitts

Kilroy

1985

J. Electrochem. Soc.

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“…More recently, McDonald (11) was able to show by mass spectroscopy the generation of substantial amounts of hydrogen and nitrogen in Li]SOCI~ batteries.…”

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Anode‐Limited Cell Reversal in Lithium‐Sulfur Oxyhalide Cells

Attia

Sarrazin

Gabriel

et al. 1984

J. Electrochem. Soc.

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In situ infrared spectroscopy and mass spectrometry were used to investigate the gas and liquid phases in lithiumsulfur oxyhalide cells driven into anode-limited reversal at 1-5 mA/cm ~. In the lithium-thionyl chloride system the species HC1, CS2, SO~, S~O, SCI~, and SO..,C1._, were identified in the gas phase and HC1, A1CI:,OH-, SOs, SO=,CI.,, and SOC1 + A1C14-in the liquid phase. A species giving rise to three absorption bands at 1337, 1070, and 665 cm-' was observed in the liquid phase of that system during anode-limited reversal only, and in the lithium sulfuryl chloride system during normal discharge and during reversal; this compound was tentatively identified as Li(SO~, SO._,CI~) § AIC14-and is analogous to the well-known complexes involving LiA1C14, SO2, and SOCI.,. The lithium-sulfuryl chloride cell behaved similarly to the thionyl chloride cell, specifically with respect to formation of SO2-and SOCl+-like species--the latter tentatively identified as SO2C1 § Indirect evidence suggests that chlorine may accumulate in both systems at -20~ but at 25~ itsaccumulation in the cells is prevented by its reaction with SO2 to form SO2C12.In the ten years since the feasibility of lithium-sulfur oxyhalide cells was first recognized (1), remarkable progress has been made in hardware development; however, their widespread use has been impeded, owing to the safety hazards associated with their relatively high energy density. Conflicting reports exist as to the cause of several explosions involving the lithium-thionyl chloride system. Explosions have been observed in anode-limited cells driven into reversal (2); a 'hazard also exists in cathode-limited cells since they contain both lithium and sulfur at the end of discharge, and the highly exothermic formation of Li2S may be possible at elevated temperatures (3, 4). In addition, poor mechanical design is suspected in some cases.The lithium-sulfuryl chloride cell which does not form any sulfur during discharge is potentially safer than Li/SOC12 (5). However, the relatively high corrosion rate of lithium in that system limits its use to special high rate reserve applications.Resolution of the unpredictable safety hazards associated with these systems may only be possible by analytical determination of their causes, and several investigations have been conducted along these lines. Istone and Brodd (6) have performed an in situ infrared study of the electrolyte of Li/SOC12 cells and observed that only two absorption bands change in intensity during normal discharge, one at 1335 cm-' due to SO~ formation, the other at 689 cm -1 which they assigned to S~O. Elemental sulfur was also seen to deposit on the spectroscopic cell walls. These authors proposed a mechanism involving formation of SO2 and $20 with subsequent decomposition of the $20 to sulfur and SO2. This mechanism had been previously rejected on the basis of stoichiometry by Schlaikjer et al. (7), who postulated instead the formation of a sulfur monoxide polymer according to the reaction 2nLi + nSOCI~ = 2nLiC1 + (SO)...

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Lithium/Thionyl Chloride Batteries

Lévy

Bro²

1994

Battery Hazards and Accident Prevention

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Sources of Pressure in Lithium Thionyl Chloride Batteries

Cited by 5 publications

References 10 publications

Physical and Chemical Characteristics of Hermetically Sealed High Rate Li / SOCl2 C‐Cells

Physical and Chemical Characteristics of Hermetically Sealed High Rate Li / SOCl2 C‐Cells

Anode‐Limited Cell Reversal in Lithium‐Sulfur Oxyhalide Cells

Lithium/Thionyl Chloride Batteries

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