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On the Possibility of Determination of Thermodynamic Functions of the Li–S Electrochemical System Using the EMF Method

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Abstract—

This work assesses the applicability of the EMF method for determination of the values of thermodynamic functions for the Li–S electrochemical system in lithium–sulfur cells with various states of charge. It is shown that the EMF method can be used for determination of the values of thermodynamic functions for the Li–S electrochemical systems in lithium–sulfur cells with various states of discharge only in the first charge–discharge cycle. The EMF method is inapplicable in the following charge–discharge cycles owing to disturbance of equilibrium in the electrochemical system due to the direct chemical interaction between sulfur and high-order polysulfides of lithium (Li2Sn, n > 4) and the metallic lithium electrode. The thermodynamic functions of the Li–S system with different sulfur reduction degree are in the following ranges: ΔG = –480…–410 kJ/mol; ΔH = –490…–420 kJ/mol; ΔS = –120…–20 J/(mol K) at the temperature of 303 K. Quantum–chemical calculations of the values of thermodynamic functions are carried out for electrochemical reduction of sulfur and lithium polysulfides. The calculated values of thermodynamic functions agree reasonably with the measured values. The thermodynamic efficiency of energy conversion is estimated for discharge of lithium–sulfur cells at 30°C; it is 93–98%.

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ACKNOWLEDGMENTS

The authors are deeply grateful to the referee for attentive consideration of the manuscript and constructive comments.

Funding

The work was financially supported by State Assignment no. AAAA-A17-117011910031-7, by the Russian Foundation for Basic Research (project no. 16-29-06190), and by the Russian Scientific Foundation (project no. 17-73-20115).

Accomplishment of the State Assignment included estimation of applicability of the EMF method of determination of thermodynamic functions of the lithium–sulfur electrochemical system and studying the regularities of variation of the thermodynamic functions of the Li–S electrochemical system in the course of the discharge of the lithium–sulfur cells with the electrolyte system of 1 M LiClO4 in sulfolane.

The funding by the Russian foundation for Basic Research included measurements of the regularities of variation of thermodynamic functions of the Li–S electrochemical system in the course of discharge of the lithium–sulfur cells with the electrolyte system of 1 M LiCF3SO3 in sulfolane.

The funding by the Russian Scientific Foundation included quantum–chemical calculations of the thermodynamic functions of electrochemical reduction of sulfur.

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Authors and Affiliations

  1. Ufa Institute of Chemistry—Subdivision of the Ufa Federal Research Centre of the Russian Academy of Sciences, 450054, Ufa, Russia

    E. V. Kuz’mina, E. V. Karaseva, N. V. Chudova, A. A. Mel’nikova & V. S. Kolosnitsyn

  2. Ufa State Petroleum Technological University, 450062, Ufa, Russia

    N. V. Chudova, A. A. Mel’nikova & V. S. Kolosnitsyn

Authors
  1. E. V. Kuz’mina
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  2. E. V. Karaseva
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  3. N. V. Chudova
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  4. A. A. Mel’nikova
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  5. V. S. Kolosnitsyn
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Contributions

The contributions of the authors are as follows: E.V. Kuz’mina (50%), E.V. Karaseva (10%), N.V. Chudova (5%), A.A. Mel’nikova (5%), V.S. Kolosnitsyn (30%).

Corresponding authors

Correspondence to E. V. Kuz’mina or V. S. Kolosnitsyn.

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Translated by M. Ehrenburg

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Kuz’mina, E.V., Karaseva, E.V., Chudova, N.V. et al. On the Possibility of Determination of Thermodynamic Functions of the Li–S Electrochemical System Using the EMF Method. Russ J Electrochem 55, 978–988 (2019). https://doi.org/10.1134/S1023193519080081

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