Abstract
A simple and convenient method has been developed for the quantitative determination of various forms of lithium in cathodic deposits formed on a stainless steel electrode during cycling, based on measuring the amount of hydrogen released during their interaction with protic solvents. The amount and ratio of electrochemically active metallic lithium, electrochemically inactive metallic lithium, and chemically bound lithium in the composition of cathode deposits formed on a steel electrode during galvanostatic cycling in sulfolane and propylene carbonate solutions of LiClO4 were determined. A method is proposed for determining the amount of an electrolyte solvent chemically reacted with metallic lithium. It has been found that, regardless of the solvent nature, the molar ratio of the reacted solvent to freshly formed lithium lies in the range of 0.84–0.85. It is assumed that the interaction of freshly formed metallic lithium with an electrolyte solvent occurs in a molar ratio of 1 : 1. The underestimated value of the reacted solvent–freshly formed lithium ratio is explained by the interaction of freshly precipitated lithium with a salt anion, which results in the formation of lithium oxide. It has been shown that the rate of destruction of sulfolane during cycling of the lithium electrode is approximately 1.5 times higher than the rate of destruction of propylene carbonate. Propylene carbonate, when interacting with freshly formed metallic lithium, forms surface films with better protective properties than sulfolane, which leads to a decrease in the rate of its interaction with metallic lithium and an increase in the Coulomb efficiency and the duration of the lithium electrode cycling.
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Funding
This work was carried out within a state task on topic no. AAAA-A20-120012090022-1 “Development of methods for improving the efficiency of energy storage in electrochemical systems of various types. Development of new electrolytes and electrode materials for supercapacitors and lithium and lithium-ion batteries, which increase their specific energy, power, and service life” and on topic no. 122031400252-2 (serial number FMRS-2022-0019) “Electrode materials and electrolyte systems for advanced energy storage devices.”
The work was performed on the equipment of the Central Collective Use Center “Chemistry.”
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Translated by E. Chernokozhin
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Ivanov, A.L., Mochalov, S.E., Karaseva, E.V. et al. Effect of the Solvent Nature on the Composition of Cathodic Deposits Formed on a Steel Electrode during Electrodeposition and Dissolution of Lithium Metal. Russ J Electrochem 58, 798–806 (2022). https://doi.org/10.1134/S1023193522090087
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DOI: https://doi.org/10.1134/S1023193522090087