Effect the temperature and lithium polysulfides on the composition of lithium cathodic deposits formed on a steel electrode

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Using our method developed earlier, we studied the effect the lithium polysulfides on the amount and ratio of electrochemically active metallic lithium, electrochemically inactive metallic lithium, and chemically formed lithium compounds into cathode deposits formed on a stainless steel electrode during galvanostatic cycling in 1М solution of LiClO4 in sulfolane at 15, 30, 45 and 60°C. It is shown that an increase in temperature leads to an increase in the Coulomb efficiency of cycling and the amount of electrochemically active metallic lithium and a decrease in the amount of electrochemically inactive metallic lithium, regardless of the presence of lithium polysulfides into electrolyte. When lithium polysulfides are introduced into the electrolyte, an increase in the Coulomb efficiency of metallic lithium cycling and a change in the ratio of various forms of lithium in cathode deposits towards an increase in electrochemically active lithium by about 1.5 times are observed. It is assumed that lithium polysulfides contribute to the dissolution of electrochemically inactive metallic lithium, forming on the electrode an interface “sulfide” film with high ionic conductivity and good protective properties, especially at elevated temperatures.

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Sobre autores

E. Karaseva

Ufa Institute of Chemistry UFRC RAS

Autor responsável pela correspondência
Email: karaseva@anrb.ru
Rússia, Ufa

S. Mochalov

Ufa Institute of Chemistry UFRC RAS

Email: karaseva@anrb.ru
Rússia, Ufa

V. Kolosnitsyn

Ufa Institute of Chemistry UFRC RAS

Email: karaseva@anrb.ru
Rússia, Ufa

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2. Fig. 1. Change in the potential of the stainless steel electrode relative to the auxiliary electrode at the initial section of the 1st cycle of cathodic deposition of lithium (a) and cathode-anodic polarization in the first cycle (b) of SS | 1M LiClO4 solution in sulfolane | Li cells at different temperatures: 1 – 15°C, 2 – 30°C, 3 – 45°C, 4 – 60°C. Cycling conditions: i = 0.2 mA/cm2; Qcath. os. = 0.5 mA h/cm2.

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3. Fig. 2. Change in the potential of the stainless steel electrode relative to the auxiliary electrode in the second (a) and tenth (b) cycles of cathode-anodic polarization of SS | 1M LiClO4 solution in sulfolane | Li cells at different temperatures: 1 – 15°C, 2 – 30°C, 3 – 45°C, 4 – 60°C. Cycling conditions: i = 0.2 mA/cm2; Qcath. os. = 0.5 mA h/cm2.

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4. Fig. 3. Effect of temperature on the Coulomb efficiency (a, c) and composition of lithium cathode deposits (b, d) during cathode-anodic cycling of a stainless steel electrode at different temperatures: 1 – 15°C, 2 – 30°C, 3 – 45°C, 4 – 60°C. a, b – in 1M LiClO4 solution in sulfolane. c, d – in 1M LiClO4 solution in sulfolane saturated with 0.25m Li2Sn. Cycling conditions: i = 0.2 mA/cm2; Qcath. os. = 0.5 mA h/cm2.

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5. Fig. 4. Diagrams of the composition of lithium cathode deposits formed on a stainless steel electrode during cycling in 1M LiClO4 solutions in sulfolane for 30 cycles at different temperatures. Cycling conditions: i = 0.2 mA/cm2; Qcath. os. = 0.5 mA h/cm2.

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6. Fig. 5. Change in the potential of the stainless steel electrode relative to the auxiliary electrode at the initial stage of the 1st cycle of cathodic deposition of lithium (a) and cathode-anodic polarization in the second cycle (b) of SS | 1M LiClO4 solution in sulfolane cells saturated with 0.25m Li2Sn | Li at different temperatures: 1 – 15°C, 2 – 30°C, 3 – 45°C, 4 – 60°C. Cycling conditions: i = 0.2 mA/cm2; Qcath. os. = 0.5 mA h/cm2.

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7. Fig. 6. Diagrams of the composition of lithium cathode deposits formed on a stainless steel electrode during cycling in a 1M LiClO4 solution in sulfolane saturated with 0.25m Li2Sn for 30 cycles at different temperatures. Cycling conditions: i = 0.2 mA/cm2; Qcath. os. = 0.5 mA h/cm2.

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