Analysis of the electrochemical impedance spectra and the structure of the solid electrolyte interphase on electrodeposited metallic lithium using the distribution of relaxation times method

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Abstract

The goal of this work was to confirm our earlier conclusion that the regularities observed during the electrodeposition of metallic lithium on copper and lithium electrodes can be associated with differences in the properties of the so-called solid electrolyte interphase (SEI), which is formed on these electrodes in contact with the electrolyte. To do this, we analyzed the electrochemical impedance spectra measured during the above processes by the method of distribution of relaxation times (DRT). It was shown that the addition of surfactants to the electrolyte such as cetyltrimethylammonium bromide and hexadecylpyridinium bromide lead to a significant change in the properties of the SEI layers and a noticeable increase in the values of the impedance components associated with the Faradaic processes on these electrodes, which indicates inhibition of the lithium electrodeposition processes and the related process of dendrite formation under these conditions. At the same time, no such impedance components were observed on the freshly formed deposit, which confirms our earlier conclusion that the effects of surfactants on dendrite formation are associated with the changes in the properties of SEI layers in the presence of surfactants rather than the surfactants adsorbing on lithium and blocking the dendrite growth.

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About the authors

S. S. Alpatov

Lomonosov Moscow State University M. V. Lomonosov, Faculty of Chemistry

Email: osemenik@elch.chem.msu.ru
Russian Federation, Moscow

F. A. Vasiliev

Lomonosov Moscow State University M. V. Lomonosov, Faculty of Chemistry

Email: osemenik@elch.chem.msu.ru
Russian Federation, Moscow

V. Kh. Aleshina

Russian University of Chemical Technology DI. Mendeleev

Email: osemenik@elch.chem.msu.ru
Russian Federation, Moscow

T. A. Vagramyan

Russian University of Chemical Technology DI. Mendeleev

Email: osemenik@elch.chem.msu.ru
Russian Federation, Moscow

O. A. Semenikhin

Lomonosov Moscow State University M. V. Lomonosov, Faculty of Chemistry

Author for correspondence.
Email: osemenik@elch.chem.msu.ru
Russian Federation, Moscow

References

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Supplementary files

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2. Fig. 1. (a) Typical electrochemical impedance hodographs measured on electrodeposited lithium metal deposited (curve 1) in the base electrolyte with the addition of hexadecylpyridinium bromide and (curve 2) in the base electrolyte without the addition of surfactant. The measurements were carried out at the open-circuit potential in the same electrolytes as the electrodeposition. The electrodeposition conditions were: (1) lithium electrode, potential of –0.07 V; (2) copper electrode, potential of –0.055 V. The lines represent the results of calculation using the model obtained by the relaxation time distribution method. The inset shows the equivalent circuit used in the analysis by the equivalent circuit method. (b) Relaxation time distribution obtained by analyzing the hodographs of Fig. 1a. The deposition was carried out (1) in the base electrolyte with the addition of hexadecylpyridinium bromide and (2) in the base electrolyte without the addition of surfactant. (c) Frequency dependences of the real (1', 2') and imaginary (1", 2") components of the impedance dependences of Fig. 1a. The lines represent the results of calculations using the model obtained by the relaxation time distribution method.

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3. Fig. 2. Relaxation time spectra obtained by processing impedance data for lithium metal deposits electrodeposited on (a) copper and (b) lithium electrodes in the presence of hexadecylpyridinium bromide (curves 1) and cetyltrimethylammonium bromide (curves 2), as well as in the base electrolyte in the absence of surfactants (curves 3).

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4. Fig. 3. Relaxation time spectra in the mid-frequency region corresponding to the impedance of the solid electrolyte interphase/SEI layers, obtained (a) in the base electrolyte without the addition of surfactant and (b) in the electrolyte with the addition of hexadecylpyridinium bromide. (1, 3) Spectra of (1) lithium and (3) copper electrode before electrodeposition; (2, 4) spectra of lithium metal deposits electrodeposited on (2) lithium and (4) copper electrodes.

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5. Fig. 4. Evolution of the relaxation time spectra obtained by processing the impedance data for lithium electrodeposited at different potentials on a substrate of (a, b) lithium and (c) copper. Electrolyte (a) with the addition of cetyltrimethylammonium bromide; (b) with the addition of hexadecylpyridinium bromide; (c) without surfactant additives. Potentials: (a) 1 – -0.03 V, 2 – -0.035 V, 3 – -0.05 V, 4 – -0.06 V; (b) 1 – -0.065 V, 2 – -0.07 V, 3 – -0.08 V; (c) 1 – -0.03 V, 2 – -0.04 V, 3 – -0.055 V. Impedances are measured at open circuit potential after lithium electrodeposition.

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