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

Klinedinst, K. A.; McLaughlin, Mary L.

doi:10.1021/je60082a017

Cited by 17 publications

(12 citation statements)

References 3 publications

(5 reference statements)

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“…The solubilities of SO.~ in SOCI~ and SOC12fLiA1C14 are given in Ref. (13). The calculated volume reduction which accompanies the Li]SOCI~ cell discharge is 0.56 mYAh (14).…”

Section: Resultsmentioning

confidence: 99%

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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“…The solubilities of SO.~ in SOCI~ and SOC12fLiA1C14 are given in Ref. (13). The calculated volume reduction which accompanies the Li]SOCI~ cell discharge is 0.56 mYAh (14).…”

Section: Resultsmentioning

confidence: 99%

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

Abraham

Pitts

Kilroy

1985

J. Electrochem. Soc.

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“…1d). Since SO 2 had a solubility of 2.47 M in SOCl 2 near room temperature at 22.3 o C and the molarity of SO 2 after the rst discharge was ~ 1.34 M, most of the SO 2 was dissolved in the electrolyte without increasing the pressure in the battery 26 . XRD and SEM imaging showed a thick layer of NaCl on the surface of the aCNS positive electrode (Fig.…”

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confidence: 99%

Rechargeable Na/Cl2 and Li/Cl2 batteries

Zhu

Tian

Tai

et al. 2021

Nature

133

167

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Sodium is a promising anode material for batteries due to its low standard electrode potential, high abundance and low cost. In this work, we report a new rechargeable ~ 3.5 V sodium ion battery using Na anode, amorphous carbon-nanosphere cathode and a starting electrolyte comprised of AlCl 3 in SOCl 2 with uoride-based additives. The battery, exhibiting ultrahigh ~ 2800 mAh/g rst discharge capacity, could cycle with a high reversible capacity up to ~ 1000 mAh/g. Through battery cycling, the electrolyte evolved to contain NaCl, various sulfur and chlorine species that supported anode's Na/Na + redox and cathode's chloride/chlorine redox. Fluoride-rich additives were important in forming a solid-electrolyte interface, affording reversibility of the Na anode for a new class of high capacity secondary Na battery. Main TextDevising new battery concepts is important to meeting society's growing demand of energy storage.Different rechargeable batteries have been developed, including lithium ion batteries (LIBs), sodium ion batteries (SIBs) and aluminum ion batteries (AIBs) [1][2][3][4][5][6][7][8][9] . Prior to the invention of secondary LIBs, a primary Li-metal battery was developed in the 1970's using thionyl chloride (SOCl 2 ) as a catholyte, Li metal as anode and amorphous carbon as the positive electrode [10][11][12][13][14][15][16] . The Li-SOCl 2 battery was attractive due to its high energy density, but did not receive sustained interest due to the lack of rechargeability 17,18 . The battery discharges through Li anode oxidation and catholyte SOCl 2 reduction into sulfur (S), sulfur dioxide (SO 2 ), and chloride ion (Cl -) on the carbon electrode 19,20 . The Clions react with Li + stripped from

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“…In early studies of Li/SOC12 batteries, it was assumed that pressure was primarily due to sulfur dioxide resulting from discharge (5-7). Although some metastable intermediates are suspected, the net electrochemical discharge is known to proceed as follows (6) 4Li -t-2SOC12--> S -t-SO2 -t-4LiC1 [1] The solubility of SO2 in electrolyte is considerable, about 4 mois/liter of electrolyte at room temperature (8).…”

Section: Discussionmentioning

confidence: 99%

Sources of Pressure in Lithium Thionyl Chloride Batteries

McDonald¹

1982

J. Electrochem. Soc.

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The generation of pressure in normalLi/SOCl2 batteries has been investigated. Hydrogen, sulfur dioxide, and nitrogen are the principal gases evolved. Reaction of lithium metal with protic species in the liquid electrolyte produces hydrogen gas on open circuit and more rapidly on discharge. Sulfur dioxide is a product of electrochemical discharge. Nitrogen, trapped in lithium metal as dissolved gas or as lithium nitride is released during discharge. In addition, smaller amounts of gas, trapped in cathode pores and adsorbed on the surface of carbon, are evolved when discharge products are deposited in the cathode. Hydrogen pressure is very sensitive to the care used in drying the electrolyte and cathodes. Alternate cycles of evacuation and backfill with SO2 eliminate much of the moisture and trapped gas from the cell prior to filling with electrolyte.

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

Cited by 17 publications

References 3 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

Rechargeable Na/Cl2 and Li/Cl2 batteries

Sources of Pressure in Lithium Thionyl Chloride Batteries

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