Russian Journal of Electrochemistry

, Volume 55, Issue 10, pp 978–988 | Cite as

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

  • E. V. Kuz’minaEmail author
  • E. V. Karaseva
  • N. V. Chudova
  • A. A. Mel’nikova
  • V. S. KolosnitsynEmail author


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%.


lithium–sulfur cell thermodynamics lithium polysulfides entropy EMF method for determination of values of thermodynamic functions DFT studies quantum-chemical study 



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


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%).


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.


This paper contains no studies with animals or people as research objects.


The authors state the absence of any conflict of interest.


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Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  • E. V. Kuz’mina
    • 1
    Email author
  • E. V. Karaseva
    • 1
  • N. V. Chudova
    • 1
    • 2
  • A. A. Mel’nikova
    • 1
    • 2
  • V. S. Kolosnitsyn
    • 1
    • 2
    Email author
  1. 1.Ufa Institute of Chemistry—Subdivision of the Ufa Federal Research Centre of the Russian Academy of SciencesUfaRussia
  2. 2.Ufa State Petroleum Technological UniversityUfaRussia

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