Calcium ‐ Ca ( AlCl4 ) 2 ‐ Thionyl Chloride Cell: Performance and Safety

Meitav, A.; Peled, E.

doi:10.1149/1.2123879

Cited by 37 publications

(44 citation statements)

References 11 publications

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“…(1)(2)(3) There is a high probability that it can be developed (4 ) as a-safe, vent-free cell which will not rupture or leak over a wide range of abusive conditions. The major drawback of the Ca-TC cell has been rapid corrosion of the calcium anode (i.e.…”

Section: Summary Of the Results Of The First Yearmentioning

confidence: 99%

Advanced Calcium-Thionyl Chloride High-Power Battery

Peled¹

1990

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Section: Summary Of the Results Of The First Yearmentioning

confidence: 99%

Advanced Calcium-Thionyl Chloride High-Power Battery

Peled¹

1990

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“…Lithium ions were assumed to be intercalated in the interchain space (2). The overall reaction of lithium intercalation was represented by the following equations (3,4) 2Li + + 2e-+ M4+X2-X~ 2 ~ (Li+)2M 4+ (X2-)3 [1] Li + + e-+ (Li+)2M 4 § (X2-)3 ~ (Li+)3M3+(X2-)3 [2] The X-X dimer is reduced in the first reaction and the transition metal in the second. Three lithiums can react with a MX3.…”

Section: T Yamamoto *'L S Kikkawa and M Koizumimentioning

confidence: 99%

“…A battery using NbSe3 was rechargeable up to x ~ 2 in Li~NbSe3 for more than 200 cycles, generating a voltage around 1.8V (3). A kind of trigonal prismatic chain exists in transition metal trichalcogenide such as TiS3 and ZrS~, having ZrSe3-type structure.…”

Section: T Yamamoto *'L S Kikkawa and M Koizumimentioning

confidence: 99%

“…The calcium-thionyl chloride battery system has been attracting considerable attention (1)(2)(3)(4)(5)(6) for its high opencircuit potentials (->3.2V), high theoretical energy density (1100 Wh/kg), broad operating temperature range~ and projected high degree of system safety. This increased safety is due to the high melting point of calcium metal (839 ~ vs. 180~ for lithium) which precludes the likelihood of difficulties traceable to a molten anode.…”

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Cathode Performance Improvement in Calcium‐Thionyl Chloride Cells

Walker

Wade

Binder

et al. 1986

J. Electrochem. Soc.

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Carbon cathode performance in ealcium-thionyl chloride cells was markedly improved with a cathode comprised of a mixture of high and low surface area carbon blacks. Addition of sulfur dioxide gas to the electrolyte further enhanced cathode performance and electrolyte conductivity. Load potentials and cathode life were nearly equal to that of the analogous lithium based system. The advantage of the calcium based system is its potential for greater safety.The calcium-thionyl chloride battery system has been attracting considerable attention (1-6) for its high opencircuit potentials (->3.2V), high theoretical energy density (1100 Wh/kg), broad operating temperature range~ and projected high degree of system safety. This increased safety is due to the high melting point of calcium metal (839 ~ vs. 180~ for lithium) which precludes the likelihood of difficulties traceable to a molten anode.

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“…Thus, bQth the calciumthionyl chloride (1)(2)(3)(4) and calcium-sulfuryl chloride (5,6) cells have been investigated during the past three years. For both these cells, solutions of lithium tetrachloroaluminate or calcium tetrachloroaluminate have been used as electrolytes.…”

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Voltammetric Reduction of Sulfuryl Chloride in the Presence of Calcium Tetrachloroaluminate

Behl

1983

J. Electrochem. Soc.

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Recently, it has been suggested (1-6) that the safety of the thionyl chloride and sulfuryl chloride cells can be significantly improved by replacing the low melting lithium anode (mp 180.7~ with a high melting calcium anode (mp 839~ Thus, bQth the calciumthionyl chloride (1-4) and calcium-sulfuryl chloride (5, 6) cells have been investigated during the past three years. For both these cells, solutions of lithium tetrachloroaluminate or calcium tetrachloroaluminate have been used as electrolytes. However, the cathode capacities in calcium cells using lithium tetrachloroaluminate solutions as electrolytes were found (5, 6) to be smaller than the cathode capacities in corresponding lithium cells. The cathode capacities in calcium cells were even smaller if solutions of calcium tetrachloroaluminate were used as electrolytes (2, 5, 6). Therefore, in order to gain an insight into the cathodic process in calcium cells, we have studied the voltammetric reduction of sulfur oxychloride solvents at smooth glassy carbon electrodes in solutions containing calcium tetrachloroaluminate. This paper summarizes our results in sulfuryl chloride solutions. ExperimentalAnhydrous lithium tetrachloroaluminate (7, 8) and anhydrous calcium chloride (9) were prepared by fusion under a flowing atmosphere of hydrogen chloride gas according to the procedures previously described. The fused salts were then treated with chlorine gas in order to oxidize any organic matter. The excess of any hydrogen chloride and chlorine gases were then removed by purging with pure dry argon gas. The anhydrous salts so prepared were solidified and stored under an argon atmosphere. Aluminum chloride (iron and water free; Fluka AG) was used as received. Sulfuryl chloride (Matheson, Coleman, and Bell Company) was refluxed over lithium metal and distilled as colorless liquid. 0.4 molar Ca(A1C14)~-SO2C12 and 1.0 molar LiA1C14-SO2C12 solutions were prepared by dissolving requisite amounts of anhydrous salts in freshly distilled sulfuryl chloride. The LiA1C14-SO2C12 and Ca(A1C14)2-SO2C12 solutions were then equilibrated with a small crystal of lithium chloride and calcium chloride, respectively, in order to neutralize traces of excess aluminum chloride, if any, in the solutions. The choice of the concentration of Ca (A1CI4)2-SO2C12 solutions used in the present study was dictated by the solubility limit (,~0.5 mol/liter) of calcium tetrachloroaluminate in sulfuryl chloride (6).A three-electrode system was used for all measurements. The reference (1 X 5 cm) and counter (3.5 X 6 cm) electrodes were both made by pressing lithium or calcium onto a nickel screen. Both electrodes were mechanically abraded and thoroughly washed with carbon tetrachloride before use. The lithium electrodes * Electrochemical Society Active Member.

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Calcium ‐ Ca ( AlCl4 ) 2 ‐ Thionyl Chloride Cell: Performance and Safety

Cited by 37 publications

References 11 publications

Advanced Calcium-Thionyl Chloride High-Power Battery

Advanced Calcium-Thionyl Chloride High-Power Battery

Cathode Performance Improvement in Calcium‐Thionyl Chloride Cells

Voltammetric Reduction of Sulfuryl Chloride in the Presence of Calcium Tetrachloroaluminate

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