Electrodeposition of lithium in the presence of surfactants

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Abstract

The aim of the work was to study the possibility of suppressing the formation of dendrites of metallic lithium during the operation of secondary lithium batteries, including those with a metallic lithium anode. The electrochemical deposition of lithium on copper and lithium substrates in the presence and absence of two surfactants, cetyltrimethylammonium bromide and hexadecylpyridinium bromide was studied by current transient and electrochemical impedance methods. A typical lithium-ion battery electrolyte based on lithium hexafluorophosphate and a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC) was used. It was shown that the presence of the so-called SEI (solid electrolyte interphase) layer on the electrode surface has a significant effect on the electrodeposition process. It was also shown that the mechanism of lithium electrodeposition on copper and lithium substrates is different. It can be assumed that the observed effect of surfactants on the dendrite formation is associated not with the adsorption of surfactants on lithium and blocking the growth of deposits, but with the effect of surfactants on the properties of the SEI layer formed on these substrates.

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About the authors

S. S. Alpatov

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

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

F. A. Vasiliev

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

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

V. Kh. Aleshina

D. I. Mendeleev Russian University of Chemical Technology

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

T. A. Vagramyan

D. I. Mendeleev Russian University of Chemical Technology

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

O. A. Semenikhin

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

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

References

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2. Fig. 1. Structural formulas of the surfactants used: (a) cetyltrimethylammonium bromide; (b) hexadecylpyridinium bromide.

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3. Fig. 2. Characteristic form of current density transients for lithium electrodeposition on electrodes made of (a) copper and (b) lithium. Potential –0.04 V (Cu) and –0.06 V (Li). Electrolyte without surfactant additives.

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4. Fig. 3. Typical impedance hodographs for lithium electrodeposition on electrodes made of (a) copper and (b) lithium. Curve 1 was measured before electrodeposition, 2 after electrodeposition, and 3 after anodic etching of the deposit. Potential –0.055 V (Cu) and –0.075 V (Li). Electrolyte without surfactant additives.

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5. Fig. 4. Evolution of current density transients as a function of potential for lithium electrodeposition on a copper electrode. (a) Electrolyte without surfactant additives; (b) with C₁₆Me₃Br additive; (c) with C₁₆PyBr additive. Potentials: (a) 1 – –0.03 V, 2 – –0.04 V, 3 – –0.05 V, 4 – –0.055 V, 5 – –0.065 V; (b) 1 – –0.03 V, 2 – –0.04 V, 3 – –0.05 V, 4 – –0.055 V, 5 – –0.07 V, 6 – –0.09 V; (in) 1 – –0.03 V, 2 – –0.04 V, 3 – –0.05 V, 4 – –0.09 V.

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6. Rice. 5. Evolution of impedance hodographs for lithium electrodeposition on a copper electrode. Electrolyte without surfactant additives. Impedances were measured after electrodeposition at potentials: 1 – 0.03 V, 2 – 0.04 V, 3 – 0.055 V.

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7. Fig. 6. Evolution of current density transients as a function of potential for lithium electrodeposition on a lithium electrode. (a) Electrolyte without surfactant additives; (b) with C₁₆Me₃Br additive; (c) with C₁₆PyBr additive. Potentials: (a) 1 – –0.04 V, 2 – –0.06 V, 3 – –0.07 V, 4 – –0.085 V; (b) 1 – –0.04 V, 2 – –0.055 V, 3 – –0.06 V, 4 – –0.07 V; (c) 1 – –0.04 V, 2 – –0.05 V, 3 – –0.065 V, 4 – –0.07 V.

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8. Fig. 7. Evolution of the impedance hodographs for lithium electrodeposition on a lithium electrode. (a) Electrolyte without surfactant additives; (b) with C₁₆Me₃Br additive; (c) with C₁₆PyBr additive. Potentials: (a) 1 – –0.07 V, 2 – –0.075 V, 3 – –0.11 V; (b) 1 – –0.03 V, 2 – –0.035 V, 3 – –0.05 V, 4 – –0.06 V; (c) 1 – –0.06 V, 2 – –0.065 V, 3 – –0.07 V, 4 – –0.08 V. The impedances were measured after lithium electrodeposition. The inset in Fig. 7(b) shows an enlarged region of the beginning of the hodographs in the high-frequency region.

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9. Fig. 8. Comparison of current density transients for electrolytes without and with surfactant additives at (a) small overvoltages and (b) significant overvoltages. (1) Electrolyte without surfactant additives; (2) with C₁₆Me₃Br additive; (3) with C₁₆PyBr additive. Potentials: (1, a) –0.04 V, (1, b) –0.06 V, (2, a) –0.04 V, (2, b) –0.06 V, (3, a) –0.04 V, (3, b) –0.07 V.

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