The effect of decalin and perfluorodecalin on Dendrite formation at metal lithium anodes During their operation

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Abstract

In this work, we studied the effect of additions of decahydronaphthalene (decalin) and its derivative, perfluorodecalin (octadecafluorodecalin), on the deposition and dissolution of lithium metal, including dendrite formation, at the anodes of secondary lithium power sources in an electrolyte based on lithium hexafluorophosphate and a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC). The study was carried out using the methods of current transients and electrochemical impedance. The results showed that, in contrast to traditional cationic surfactants cetyltrimethylammonium bromide and hexadecylpyridinium bromide, which we studied earlier, decalin and perfluorodecalin demonstrate specific interaction with the surface of the lithium electrode. Moreover, the interaction with decalin is so strong that it actually blocks the processes of both deposition and anodic dissolution of lithium at the surface of the lithium electrode. The interaction of perfluorodecalin with the lithium surface turned out to be weaker. As a result, perfluorodecalin does not interfere with the cycling of the metal lithium anode, but at the same time shows an inhibitory effect on the dendrite formation. In the electrolyte with the addition of perfluorodecalin, lithium anode was able to undergo more than 80 charge-discharge cycles with a Coulomb efficiency of 70–80%, while without the additive, the number of cycles was less than 40, and the Coulomb efficiency was 60% or lower.

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About the authors

S. S. Alpatov

M.V. Lomonosov Moscow State University

Email: osemenik@elch.chem.msu.ru

Department of Chemistry

Russian Federation, Moscow

F. A. Vasiliev

M.V. Lomonosov Moscow State University

Email: osemenik@elch.chem.msu.ru

Department of Chemistry

Russian Federation, Moscow

O. A. Semenikhin

M.V. Lomonosov Moscow State University

Author for correspondence.
Email: osemenik@elch.chem.msu.ru

Department of Chemistry

Russian Federation, Moscow

References

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2. Fig. 1. Impedance hodographs measured on electrodes made of (a) lithium and (b) copper before deposition of metallic lithium at a potential of –0.03 V in the presence of additives of (1) perfluorinated and (2) non-fluorinated decalin.

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3. Fig. 2. Impedance hodographs measured on electrodes made of (a) lithium and (b) copper after deposition of metallic lithium at a potential of –0.03 V in the presence of additives of (1) perfluorinated and (2) non-fluorinated decalin.

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4. Fig. 3. Current density transients measured during the deposition of metallic lithium on (a) copper and (b) lithium electrodes at a potential of –0.03 V in the following electrolytes: (1) with the addition of decalin, (2) with the addition of perfluorodecalin, (3) without additives.

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5. Fig. 4. Current density transients measured during lithium metal deposition: (a, b) on the copper electrode in the electrolyte with the addition of decalin, (c) on the copper electrode in the electrolyte with the addition of perfluorodecalin, (d) on the lithium electrode in the electrolyte with the addition of decalin (curves 1, 2) and with the addition of perfluorodecalin (curves 3, 4, 5). Potentials: (a, b) 1 – –0.03 V, 2 – –0.025 V, 3 – –0.04 V, 4 – –0.6 V, 5 – –0.1 V; (c) 1 – –0.03 V, 2 – –0.06 V, 3 – –0.095 V; (d) 1 – –0.085 V, 2 – –0.06 V, 3 – –0.03 V, 4 – –0.06 V, 5 – –0.1 V.

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6. Fig. 5. Galvanostatic charge-discharge curves obtained for galvanostatic deposition-dissolution of lithium on a copper electrode at a current density of 0.1 mA/cm² (1) in a standard electrolyte without additives and (2) in an electrolyte with the addition of perfluorinated decalin. Cycle No. 7.

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