The electrochemistry of the Li/SOCl2 cell—I. The passivation of the cathode

Hagan, W.P.; Hampson, N.A.; Packer, Randall K.

doi:10.1016/0013-4686(86)87038-4

Cited by 10 publications

(7 citation statements)

References 5 publications

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“…For cathodic overpotentials, the area corrected log Rct vs. potential yields a slope of 112 mV/decade, indicating a charge transfer coefficient of 0.26 for a two-electron charge transfer. Our value of a can be compared with that found by Hagan et al (12) for SOC12 reduction, which was 0.16.…”

Section: Resultssupporting

confidence: 68%

“…A platinum electrode with a surface area of 0.0078 cm 2 set in a Teflon tube, was used as the working electrode. The platinum electrode was cleaned before each experiment by rubbing it with diamond pastes of three different particle sizes (3,12, and 24 ~tm), soaking it in ethanol, and then drying under vacuum.…”

Section: Methodsmentioning

confidence: 99%

“…At this time, two hypothesis concerning the rate-determining step of the reduction were proposed (11): (i) either the diffusion of SO2C12 occurred through a dense layer of LiC1, with a value of the diffusion coefficient of 10 10 cm 2 . s-~ (it) or the LiC1 film presented a low porosity and diffusion occurred in the grain boundaries.We supposed the latter was more reasonable since the formation of SO2 during the reduction could promote LiC1 solubility at the electrode/electrolyte interface (12)(13)(14).This paper deals with the formation of the passivating film during SO2C12 reduction at a platinum microelectrode. This growth is followed by the impedance method which enables one to compare the texture of the film formed in both SO2C12, LiA1C14 2M and SO2C12-solvate mixed electrolytes.…”

mentioning

confidence: 98%

“…We supposed the latter was more reasonable since the formation of SO2 during the reduction could promote LiC1 solubility at the electrode/electrolyte interface (12)(13)(14).…”

mentioning

confidence: 99%

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The Impedance of the Cathodic Electrode in SO 2Cl2 ‐ Solvate Mixed Electrolytes

Lojou¹,

Messina²,

Chenebault³

et al. 1991

J. Electrochem. Soc.

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Impedance measurements were carried out at a platinum electrode in SQC12-solvate mixed electrolytes. Impedance loci were recorded over a range of frequencies at several surimposed potentials. The results confirm the growth of a passivating film as the reduction proceeds. Great differences for the texture of this film were obtained between SO2C12 electrolyte and SO2C12-solvate mixed electrolytes, and it was possible in some cases to remove the passivating film by applying low anodic potentials to the electrode.Lithium/liquid cathode systems have received considerable interest in recent years for space and military applications due to their high energy and power densities (1). Among these systems, LiA1C14, 3SO2 solvate has been used for secondary Li/SO2 cells (2, 3) or for solid cathode systems (4). A recent work (5), has shown that this electrolyte was also suitable for fundamental studies of the reduction of SO2C12 because of its stability over a large range of potentials. Furthermore, using the solvate provided improvements in discharge characteristics of Li/SO2C12 cells due to the high solvate conductivity over a large range of temperatures (6).The generally accepted mechanism for SO2C12 reduction can be written as follows SO2Cl2 + 2e ---> SO2 + 2C1As solid LiC1 precipitated during discharge (7), many studies have dealt with optimal solutions to the cathode polarization problems (8-10). However, a better understanding of the reaction mechanisms is necessary, especially when LiA1C14, 3SO2 solvate is used as a cosolvent in SO2Cl2, in order to improve the performance of high rate cells.A previous investigation, devoted to SO2C12 reduction in the solvate, emphasized that the reduction was controlled by a diffusion process through a buildup of LiC1 (5). At this time, two hypothesis concerning the rate-determining step of the reduction were proposed (11): (i) either the diffusion of SO2C12 occurred through a dense layer of LiC1, with a value of the diffusion coefficient of 10 10 cm 2 . s-~ (it) or the LiC1 film presented a low porosity and diffusion occurred in the grain boundaries.We supposed the latter was more reasonable since the formation of SO2 during the reduction could promote LiC1 solubility at the electrode/electrolyte interface (12)(13)(14).This paper deals with the formation of the passivating film during SO2C12 reduction at a platinum microelectrode. This growth is followed by the impedance method which enables one to compare the texture of the film formed in both SO2C12, LiA1C14 2M and SO2C12-solvate mixed electrolytes. The possibility of removing the passivating film by applying anodic potentials to the cathodic collector is then examined. Finally, the reoxidation process of SO2C12 in the different electrolytes are compared using an intensiostatic method. Experimental ProcedureElectrolytes.--All experiments were carried out in an argon-filled glove box at a temperature of 20~ * Electrochemical Society Active Member.A solvate of composition 3SO~, LiA1C14, which presents a conductivity of 92.10 -3 ~ ~ 9 ...

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Section: Resultssupporting

confidence: 68%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 98%

“…We supposed the latter was more reasonable since the formation of SO2 during the reduction could promote LiC1 solubility at the electrode/electrolyte interface (12)(13)(14).…”

mentioning

confidence: 99%

See 2 more Smart Citations

The Impedance of the Cathodic Electrode in SO 2Cl2 ‐ Solvate Mixed Electrolytes

Lojou¹,

Messina²,

Chenebault³

et al. 1991

J. Electrochem. Soc.

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“…0.19 V decade À1 , observed for ZnOCC0.5/BDD, is in line with those reported for some perovskites (0.17 to 0.23 V decade À1 ) 114 and is encouraging when taking into account the doubling of the Tafel slope assumed for electrodes with a porous structure. 115 The anomalous Tafel slope-values for the ZnOC0.005 and ZnOC0.1 samples are attributed to the influence of adsorption processes 116 and gas bubble adherence to the electrode surface affecting electrode kinetics. 117 We conclude that ZnOC0.5 composites can be used as a platinum substrate for oxygen evolution, as the porosity and ZnO content result in a synergetic electrocatalytic effect.…”

Section: Electrochemical Behaviour Of Zno-carbon Compositesmentioning

confidence: 97%

Sustainable one-pot integration of ZnO nanoparticles into carbon spheres: manipulation of the morphological, optical and electrochemical properties

Patrinoiu

Calderón-Moreno

Bı̂rjega

et al. 2016

Phys. Chem. Chem. Phys.

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ZnO-carbon composite spheres were synthesized via starch hydrothermal carbonization (HTC) in the presence of a soluble zinc salt (acetate), followed by thermal processing under an argon atmosphere. Besides sustainability, the one-pot procedure represents a scalable synthesis of tailored carbon-metal oxide spheres with a structurally-ordered carbon matrix obtained at a relatively low temperature (700 °C). The ability of zinc cations to develop different linkages with starch's hydrophilic functional groups and to act as external nucleators determines an increase in HTC yield; the effect is obvious even in the presence of small concentrations of zinc in the reaction medium (0.005 M), thus providing a way to improve the carbonization process efficiency. It is also shown that zinc content is the control vector of the spherical composite's properties: a variation from 0.3 to 4.8 at% not only induces a variation in their size (200 nm-10 μm), interconnectivity (from disperse spheres to necklace-like aggregations), surface area and connected porosity (from micro- to mesoporosity), but also of their electrochemical and white light adsorption and emission features. Since the variation in zinc content is made by a simple adjustment of the raw material concentrations, the functionality of these carbon-based materials can be modulated in a straightforward manner.

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