The kinetics of the reduction of thionyl chloride

Schlaikjer, C.

doi:10.1016/0378-7753(89)80024-2

Cited by 8 publications

(2 citation statements)

References 38 publications

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“…Similarly, discharge products such as sulfur and LiCl can deposit on the electrodes and form passivation layers at low SoCs. 42 Thus, the active surface area of the electrodes is reduced, causing an increase in the overall impedance response. Additionally, acquiring KKcompatible spectra at very low SoCs is challenging because of the lack of stability and linearity of the battery processes.…”

Section: Resultsmentioning

confidence: 99%

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl₂) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)

Katırcı,

Civan,

Zabara

et al. 2024

J. Electrochem. Soc.

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Electrochemical Impedance Spectroscopy (EIS) has been utilized as an in situ, non-destructive diagnostic tool for the comprehensive electrochemical characterization of lithium thionyl chloride (Li/SOCl2) batteries. Li/SOCl2 batteries come in various geometries or architectures tailored for the application area and required specifications. In this study, detailed EIS studies of spiral and bobbin-type Li/SOCl2 batteries are performed at different temperatures to investigate the impedance response, calculate the activation energy of various processes, and observe the effect of geometry. An extensive comparison between the two geometries reveals that the processes can be differentiated by their time constants and capacitances. It was observed that the current collector impedance masks the high-frequency response of bobbin-type at elevated temperatures with similar Li redox processes in the middle-frequency region. Additionally, transmission line fit is performed on the bobbin type to investigate diffusion-related cathodic processes.

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Section: Resultsmentioning

confidence: 99%

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl₂) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)

Katırcı,

Civan,

Zabara

et al. 2024

J. Electrochem. Soc.

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“…The rate of secondary film growth strongly depends on temperature, 20 electrolyte concentration, 14,20 and on the type of electrolyte additives. 15,21,22 For a 1.5 M LiAlCl 4 solution without additives and at ambient temperature, one finds on average the following values of the secondary-film thickness 3,7,8,15 : about 1 m after 1 day, 10 m after 1 month, and 20 m after 1 year of storage.…”

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confidence: 99%

Time Evolution of the Impedance Response of a Passive Film: A Simple Application to the Li / SOCl2 system

Gaberšček

Pejovnik

1999

J. Electrochem. Soc.

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In the 1970s and the beginning of the 1980s the passive film formed on lithium in SOCl 2 -based solutions was a subject of numerous investigations, primarily because it was regarded as a cause of the so-called voltage-delay phenomenon, which, at that time, was a major drawback of the Li/SOCl 2 batteries. To many researchers, however, the system remained interesting even after the voltage-delay problem had been solved (by different electrolyte additives and/or modifications). The persisting interest in this particular lithium system can be explained by several facts: (i) in this system the lithium passive film has a simple composition (basically LiCl), (ii) the electrochemical properties (e.g., the impedance response) of this film have been considered simple to model, (iii) the film electrochemical properties show big and hence easy-to-measure variation with storage time, and (iv) during investigation of the "voltage-delay phenomenon," a huge amount of data using many different techniques were gathered, many of which have remained unexplained or even in direct contradiction. The present paper is an attempt to clarify several of these inconsistencies, particularly those concerning the impedance spectroscopy and related measurements of the passive film.The techniques used to study the spontaneous nucleation and growth of the passive film under consideration have been the potential sweep and step (or pulse) experiments, 1-5 impedance spectroscopy measurements, 6-11 microcalorimetry, 9,12 scanning electron microscopy (SEM), 7,10,13-15 measurements of weight gain of a Li electrode during storage in the electrolyte, 16 and the isotope method. 8 With regard to the kinetics of the initial coverage of the lithium surface with a passive film, most authors have given qualitative estimations such as, "Immediately 4,8,17 after its contact with the electrolyte, the Li surface is covered with a thin passivating film." A more quantitative result was obtained by Hedges et al. 2 who, in microelectrode studies of the Li/Li ϩ couple, found that "a period on open circuit of 100 s is long enough for the formation of a film of thickness sufficient to inhibit corrosion..." (In that experiment 1.7 M solution of LiAlCl 4 in SOCl 2 was used.) Even more specific results were obtained by Moshtev et al., 3 who found it possible to determine the moment when the lithium surface was 100% covered with a thin protective film using the galvanostatic pulse technique. Although not explicitly given in Ref. 3, one may recalculate from Fig. 2 and 3 of that paper that the coverage was completed about 30-40 min after lithium had been exposed to the electrolyte. At that moment the calculated average film thickness was 3.2 nm. Moshtev et al. 3 also reported that after the Li surface had been covered, the dense primary film grew thicker with storage time to reach a thickness of about 10-30 nm within a period of 6 h. Similar results were obtained by Holleck and Brady, 4 who reported that the primary film reached a thickness of 30 nm within 1-20 h after the ex...

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Sulfur Compounds

Weil¹,

Sandler²

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Sulfur is a component of many compounds. Carbon sulfides, thiophosgenes, trichloromethanesulfenyl chloride, hydrogen sulfide, hydrogen polysulfides (sulfanes), sulfur halides and oxyhalides, sulfur nitrides, sulfur oxides, sulfur oxygen acids and their salts, thiocyanic acid and its salts, methanesulfonyl chloride, and methanesulfonic acid are all discussed, along with properties, manufacture, shipment and storage, economic aspects, analytical methods, grades and specifications, health and safety, and uses.

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The kinetics of the reduction of thionyl chloride

Cited by 8 publications

References 38 publications

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl₂) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl₂) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)

Time Evolution of the Impedance Response of a Passive Film: A Simple Application to the Li / SOCl2 system

Sulfur Compounds

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The kinetics of the reduction of thionyl chloride

Cited by 8 publications

References 38 publications

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl2) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl2) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)

Time Evolution of the Impedance Response of a Passive Film: A Simple Application to the Li / SOCl2 system

Sulfur Compounds

Contact Info

Product

Resources

About

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl₂) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)

Observing the Effect of Architecture on Spiral and Bobbin Lithium Thionyl Chloride (Li/SOCl₂) Batteries with Temperature-Dependent Electrochemical Impedance Spectroscopy (EIS)