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Title: Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF3SO2)2N at High Current Densities

Abstract

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteries with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl2. Hence, ethereal solutions of Mg(TFSI)2 salt with MgCl2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm-2 and an areal capacity of ~0.4 mAh cm-2, which is closemore » to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI- anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [1];  [1];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  3. Univ. of Illinois, Chicago, IL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1418163
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 33; Journal Issue: 37; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; metal anode

Citation Formats

Yoo, Hyun Deog, Han, Sang-Don, Bolotin, Igor L., Nolis, Gene M., Bayliss, Ryan D., Burrell, Anthony K., Vaughey, John T., and Cabana, Jordi. Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF3SO2)2N– at High Current Densities. United States: N. p., 2017. Web. doi:10.1021/acs.langmuir.7b01051.
Yoo, Hyun Deog, Han, Sang-Don, Bolotin, Igor L., Nolis, Gene M., Bayliss, Ryan D., Burrell, Anthony K., Vaughey, John T., & Cabana, Jordi. Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF3SO2)2N– at High Current Densities. United States. doi:10.1021/acs.langmuir.7b01051.
Yoo, Hyun Deog, Han, Sang-Don, Bolotin, Igor L., Nolis, Gene M., Bayliss, Ryan D., Burrell, Anthony K., Vaughey, John T., and Cabana, Jordi. Wed . "Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF3SO2)2N– at High Current Densities". United States. doi:10.1021/acs.langmuir.7b01051. https://www.osti.gov/servlets/purl/1418163.
@article{osti_1418163,
title = {Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF3SO2)2N– at High Current Densities},
author = {Yoo, Hyun Deog and Han, Sang-Don and Bolotin, Igor L. and Nolis, Gene M. and Bayliss, Ryan D. and Burrell, Anthony K. and Vaughey, John T. and Cabana, Jordi},
abstractNote = {The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteries with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl2. Hence, ethereal solutions of Mg(TFSI)2 salt with MgCl2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm-2 and an areal capacity of ~0.4 mAh cm-2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI- anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.},
doi = {10.1021/acs.langmuir.7b01051},
journal = {Langmuir},
number = 37,
volume = 33,
place = {United States},
year = {2017},
month = {6}
}

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