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Mg Anode Passivation Caused by the Reaction of Dissolved Sulfur in Mg–S Batteries

Laskowski, Forrest A. L. and Stradley, Steven H. and Qian, Michelle D. and See, Kimberly A. (2021) Mg Anode Passivation Caused by the Reaction of Dissolved Sulfur in Mg–S Batteries. ACS Applied Materials & Interfaces, 13 (25). pp. 29461-29470. ISSN 1944-8244. doi:10.1021/acsami.1c02788.

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As Li-ion battery optimization approaches theoretical limits, interest has grown in designing next-generation batteries from low-cost earth-abundant materials. Mg–S batteries are promising candidates, exhibiting widespread abundance of elemental precursors and a relatively large theoretical energy density albeit at lower cell voltage. However, Mg–S batteries exhibit poor reversibility, in part due to interactions between dissolved polysulfides and the Mg anode. Herein, we employ electrochemical experiments using Ag₂S quasi-reference electrodes to probe the interactions between Mg anodes and dissolved polysulfides. We show that Mg²⁺ reduction (charging) is impeded in the presence of polysulfides, while Mg metal oxidation (discharging) remains facile. Large reduction overpotentials arise due to the formation of a passivation layer on the anode surface, likely composed primarily of MgS. The passivation layer is removed under oxidative conditions but quickly reforms during reduction. We discover that dissolved S8 influences the rate of MgS formation by shifting the polysulfide disproportionation equilibria. Shorter-chain polysulfides react more readily than longer-chain polysulfides at the Mg electrode, and thus, film formation is mediated by the electrochemical generation of shorter-chain polysulfide species.

Item Type:Article
Related URLs:
URLURL TypeDescription
Laskowski, Forrest A. L.0000-0001-8909-483X
Qian, Michelle D.0000-0002-4815-1014
See, Kimberly A.0000-0002-0133-9693
Additional Information:© 2021 American Chemical Society. Received: February 9, 2021; Accepted: May 28, 2021; Published: June 18, 2021. F.A.L.L. acknowledges the support of the Arnold and Mabel Beckman Foundation via a 2020 Arnold O. Beckman Postdoctoral Fellowship in Chemical Sciences. The authors thank Andrew J. Martinolich, Seong Shik Kim, and Sarah C. Bevilacqua for their guidance and insightful scientific input. Author Contributions. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. The authors declare no competing financial interest. The data that support the findings of this study are available from the corresponding author upon reasonable request.
Subject Keywords:Mg−S battery, Mg SEI, magnesium polysulfides, divalent batteries, Mg corrosion
Issue or Number:25
Record Number:CaltechAUTHORS:20210628-191053554
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Official Citation:Mg Anode Passivation Caused by the Reaction of Dissolved Sulfur in Mg–S Batteries. Forrest A. L. Laskowski, Steven H. Stradley, Michelle D. Qian, and Kimberly A. See. ACS Applied Materials & Interfaces 2021 13 (25), 29461-29470; DOI: 10.1021/acsami.1c02788
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109628
Deposited By: George Porter
Deposited On:28 Jun 2021 23:23
Last Modified:06 Jul 2021 21:32

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